Accepted in the Journal of Physical Chemistry A, with my fingers crossed for pulling off the rare double-header in an upcoming print edition of the journal (having missed it by three intermediate articles with the Cs2B12H12 and HMX papers back in 2006 (you’d keep track, too). A fortuitous overlap of scheduled defense dates between P. Hakey, Ph.D. and M. Hudson, A.B.D.). A brief summary of interesting points from this study is provided below, including what I think is a useful point about how to most easily interpret AND represent solid-state vibrational spectra for publications.
1. AS USUAL, YOU CANNOT USE GAS-PHASE CALCULATIONS TO ASSIGN SOLID-STATE TERAHERTZ SPECTRA. It will take a phenomenal piece of data and one helluvan interpretation to convince me otherwise. As a more subtle point (for those attempting an even worse job of vibrational mode assignment), if the molecule exists in its protonated form in the solid-state, do not use the neutral form for your gas-phase calculation (this is a point that came up as part of an MDMA re-assignment published (and posted here) previously).
2. It is very difficult to find what I would consider to be “complete data sets” for molecules and solids being studied by spectroscopic and computational methods. For many molecular solids, the influences of thermal motion are not important to providing a proper vibrational analysis by solid-state density functional theory methods. Heating a crystal may make spectral lines broader, but phase changes and unusual spectral features do not often result when heating a sample from cryogenic (say, liquid nitrogen) to room temperature. Yes, there are thousands of cases where this is not true, but several fold more cases where it is. We are fortunate to live in a temperature regime where characterization is reasonably straightforward and yet we can modify a system to observe its subtle changes under standard laboratory conditions. The THz spectrum of S-(+)-Ketamine Hydrochloride gets a bit cleaner upon cooling, which makes the assignment easier. As the ultimate goal is to be able to characterize these systems in a person’s pocket instead of their liquid nitrogen thermos, the limited observed change to the spectrum upon cooling is important to note.
3. Crystal06 vs. DMol3 – This paper contains what is hoped to be a level, pragmatic discussion about the strengths and weaknesses of computational tools available to terahertz spectroscopists for use in their efforts to assign spectra. This type of discussion is, as a computational chemist using tools and not developing tools, a touchy subject to present on not because of the finger-pointing of limitations with software, but because the Crystal06 team and Accelrys (through Delley’s initial DMol3 code) clearly are doing things that the vast majority of their users (myself included) could in no way do by themselves. The analysis for the theory-minded terahertz spectroscopist is presented comparing two metrics – speed and functionality (specifically, infra-red intensity prediction). What is observed as the baseline is that both DMol3 and Crystal06 make available density functionals and basis sets that, when used at high levels of theory and rigorous convergence criteria, produce simulated terahertz spectra with vibrational mode energies that are in good (if not very good) agreement with each other. For the terahertz spectroscopist, Crystal06 provides as output (although this is system size- and basis set size-dependent) rigorous infrared intensity predictions for vibrational modes, inseparable from mode energy as “the most important” pieces of information for mode assignments. While DMol3 does not produce infrared intensities (the many previous terahertz papers I’ve worked on employed difference-dipole calculations that are, at best, a guesstimate), DMol3 produces very good mode energy predictions in 1/6th to (I’ve seen it happen) 1/10th the time of a comparable Crystal06 calculation. This is the reason DMol3 has been the go-to program for all of the neutron scattering spectroscopy papers cited on this blog (where intensity is determined by normal mode eigenvectors, which are provided by both (and any self-respecting quantum chemical code) programs).
Now, it should be noted that this difference in functionality has NOTHING to do with formalism. Both codes are excellent for what they are intended to do. To the general assignment-minded spectroscopist (the target audience of the Discussion in the paper), any major problem with Crystal06 likely originates with the time to run calculations (and, quite frankly, the time it takes to run a calculation is the worst possible reason for not running a calculation if you need that data. Don’t blame the theory, blame the deadline). In my past exchanges with George Fitzgerald of Accelrys, the issue of DMol3 infrared intensities came up as a feature request that would greatly improve the (this) user experience and Dr. Fitzgerald is very interested (of course) in making a great code that much better. Neither code will be disappearing from my toolbox anytime soon.
4. The Periodicity Of The Molecular Solid Doesn’t Care What The Space Group Is – One of the more significant problems facing the assignment-minded spectroscopist is the physical description of molecular motion in a vibrational mode. In the simplest motions involving the most weakly interacting molecules, translational and rotational motions are often quite easy to pick out and state as such. When the molecules are very weakly interacting, often the intramolecular vibrational modes are easy to identify as well, as they are largely unchanged from their gas-phase descriptions. In ionic solids or strongly hydrogen-bonded systems, it is often much harder to separate out individual molecular motions from “group modes” involving the in- and out-of-phase motions of multiple molecules. In the unit cells of molecular solids, it can be the case that these group modes appear, by inspection, to be extremely complicated, sometimes too involved to easily describe in the confines of a table in a journal article.
S-(+)-Ketamine Hydrochloride is one such example where a great simplification in vibrational mode description comes from thinking, well, “outside the box.” The image below shows two cells and the surrounding molecules of S-(+)-Ketamine Hydrochloride. As it is difficult to see why the mode descriptions are complex from just an image, assume that I am right in this statement of complexity. Part of this complexity comes from the fact that the two molecules in the unit cell are not strongly interacting, instead packed together by van der Waals and dispersion forces more than anything else. The key to a greatly simplified assignment comes from the realization that the most polar fragments of these molecules are aligned on the edges of the unit cell.
An alternate view of molecular vibrational motion comes from considering not the contents of the defined unit cell but the hydrogen-bonding and ionic bonding arrangement that exists between pairs of molecules between unit cells. The colorized image below shows two distinct chains (red and blue) that, when the predicted vibrational modes are animated, become trivial to characterize as the relative motions of a hydrogen/ionic-bonded chain. Rotational motions appear as spinning motions of the chains, translational motions as either chain sliding motions or chain breathing modes. It appears as a larger macromolecule undergoing very “molecular” vibrations. In optical vibrational spectroscopy, selection rules and the unit cell arrangement do not produce in- and out-of-phase motions of the red and blue chains, as only one “chain” exists in the periodicity of the unit cell. In neutron scattering spectroscopy, these relative motions between red and blue would appear in the phonon region. This same discussion was had, in part, in a previous post on the solid-state terahertz assignment of ephedrine (with a nicer picture).
So, look at the cell contents, then see if there’s more structure than crystal packing would indicate. It greatly simplifies the assignment (which, in turn. greatly simplifies the reader’s digestion of the vibrational motions).
Patrick M. Hakey, Damian G. Allis, Matthew R. Hudson, Wayne Ouellette, and Timothy M. Korter
Department of Chemistry, Syracuse University, Syracuse, New York 13244-4100
Abstract: The terahertz (THz) spectrum of (S)-(+)-ketamine hydrochloride has been investigated from 10 to 100 cm-1 (0.3-3.0 THz) at both liquid-nitrogen (78 K) and room (294 K) temperatures. Complete solid-state density functional theory structural analyses and normal-mode analyses are performed using a single hybrid density functional (B3LYP) and three generalized gradient approximation density functionals (BLYP, PBE, PW91). An assignment of the eight features present in the well-resolved cryogenic spectrum is provided based upon solid-state predictions at a PW91/6-31G(d,p) level of theory. The simulations predict that a total of 13 infrared- active vibrational modes contribute to the THz spectrum with 26.4% of the spectral intensity originating from external lattice vibrations.
Available as an ASAP in The Journal of Physical Chemistry A. As a general rule in computational chemistry, the smaller the molecule, the harder it is to get right. As a brief summary, parabanic acid has several interesting properties of significance to computational chemists as both a model for other systems containing similar sub-structures and as a complicated little molecule in its own right.
1. The solid-state spectrum requires solid-state modeling. This should be of no surprise (see the figure below for the difference in solid-state (top) and isolated-molecule (bottom)). This task was undertaken with both DMol3 and Crystal06, with DMol3 calculations responsible for the majority of the analysis of this system (as has always been the case in the neutron studies reported on this site).
2. The agreement in the hydrogen-bonded N-H…O vibrations is, starting from the crystal structure, in poor agreement with experiment. You’ll note the region between 750 and 900 cm-1 is a little too high (and for clarification, the simulated spectrum is in red below). According to the kitchen sink that Matt threw at the structure, the problem is not the same anharmonicity one would acknowledge by Dr. Walnut’s “catalytic handwaving” approach to spectrum assignment (Dr. Walnut does not engage in this behavior, rather endeavors to find it in others where it should not be).
3. The local geometry of the hydrogen-bonding network in this molecular solid leads to notable changes in parabanic acid structure that, in turn, leads to the different behavior of the N-H…O vibrational motions. There is one potentially inflammatory comment in the Conclusions section that results from this identification. The parabanic acid molecule is, at its sub-structure, a set of three constrained peptide linkages that under go subtle but vibrationally-observable changes to their geometry because of crystal packing and intermolecular hydrogen bond formation. This means that the isolated molecule and solid-state forms are different and that peptide groups are influenced by neighboring interactions.
So, why should one care? Suppose one is parameterizing a biomolecular force field (CHARMM, AMBER, GROMOS, etc.) using bond lengths, bond angles, etc., for the amino acid geometry and vibrational data for some aspect of the force constant analysis. The structural data for these force fields often originates with solid-state studies (diffraction results). This means, to those very concerned with structural accuracy, that a geometry we know to be influenced by solid-state interactions is being used as the basis for molecular dynamics calculations that will NOT be used in their solid-state forms. Coupled with the different spectral properties due to intermolecular interactions, the description being used as the basis for the biomolecular force field likely being used in solution (solvent box approaches) is based on data in a phase where the structure and dynamics are altered from their less conformationally-restricted counterpart (in this case, solid-state).
A subtle point, but that’s where applied theoreticians do some of their best work.
Matthew R. Hudson, Damian G. Allis, and Bruce S. Hudson
Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University, Syracuse, New York 13244-4100
Abstract: The incoherent inelastic neutron scattering spectrum of parabanic acid was measured and simulated using solid-state density functional theory (DFT). This molecule was previously the subject of low-temperature X-ray and neutron diffraction studies. While the simulated spectra from several density functionals account for relative intensities and factor group splitting regardless of functional choice, the hydrogen-bending vibrational energies for the out-of-plane modes are poorly described by all methods. The disagreement between calculated and observed out-of-plane hydrogen bending mode energies is examined along with geometry optimization differences of bond lengths, bond angles, and hydrogen-bonding interactions for different functionals. Neutron diffraction suggests nearly symmetric hydrogen atom positions in the crystalline solid for both heavy-atom and N-H bond distances but different hydrogen-bonding angles. The spectroscopic results suggest a significant factor group splitting for the out-of-plane bending motions associated with the hydrogen atoms (N-H) for both the symmetric and asymmetric bending modes, as is also supported by DFT simulations. The differences between the quality of the crystallographic and spectroscopic simulations by isolated-molecule DFT, cluster-based DFT (that account for only the hydrogen-bonding interactions around a single molecule), and solid-state DFT are considered in detail, with parabanic acid serving as an excellent case study due to its small size and the availability of high-quality structure data. These calculations show that hydrogen bonding results in a change in the bond distances and bond angles of parabanic acid from the free molecule values.
On October 4, a concert is planned with “The Excelsior Cornet Band”. “The Excelsior Cornet Band” is New York State’s only authentic Civil War brass band. Founded in 2001, the band consists of a group of upstate New York musicians who are dedicated to the performance of original Civil War music on actual antique brass band instruments of the 1860’s period. They will be performing their Abraham Lincoln Program on Sun., Oct 4 at 2 pm on the second floor of the Library.
With my trusty Olympus LS-10 (Linear PCM) Recorder set to PCM (44.1kHz/16bit) mode (additional settings: Low Cut OFF, Mic Sensitivity HIGH, recorder placed on the drums side of the band 20 feet away from any instruments) and my Canon Powershot SD780 IS (digital ELPH) set to HD video mode (the only canon in attendance), I managed to capture an official bootleg of a Civil War Band in performance, certainly one of the few in history. Regretfully, the video is only of the first 25 minutes of the performance.
Our fearless leader Jeff Stockham provided a considerable amount of text about the occasion and the music of the occasion (as 2009 is, now was, the bicentennial year of President Abraham Lincoln’s birth) that I decided was best retained in the full recording. As this was too much to type out (and it is quite clear in the recordings anyway), I have included brief comments on the pieces in the concert below with relevant links to web content about pieces, original performers, and significant historical figures.
The set list is below. The full MP3 album (320 kpbs) of the performance is available for download at the link “1″ below (all song and album data should appear with an import to iTunes or related). In .tar.gz format. Most modern operating systems will open this file automatically to provide the .mp3 files. If not, I suspect you’re running an older version of Windows and should, therefore, download 7-Zip, Winzip, or related. Link “2″ contains the unseperated MP3 audio of the concert (the talk between music is hard to hear. The .tar.gz file has the spoken sections amplified). Link “3″ is of the .mov file of the first 25 minutes of the performance (much faster if you download to desktop). For both the MP3 and MOV files, please save to your own machine instead of streaming from my website (right-click over the link and “Save As,” “Save Link As,” etc.).
Henry Clay Whitney’s recollection of a comment from Abraham Lincoln – all other pleasures had a utility, but that music was simply a pleasure and nothing more, and that he fancied that the creator, after providing all the mechanism for carrying on the world, made music as a simple, unalloyed pleasure…. This text is copied from www.abrahamlincolnsclassroom.org.
“I am loath to close. We are not enemies, but friends. We must not be enemies. Though passion may have strained it must not break our bonds of affection. The mystic chords of memory, stretching from every battlefield and patriot grave to every living heart and hearthstone all over this broad land, will yet swell the chorus of the Union, when again touched, as surely they will be, by the better angels of our nature.” – Abraham Lincoln’s close of his first inaugural address.
03. Introduction to “Old Joe Hooker Quickstep” – 2:37
Joseph Hooker (left) and Robert E. Lee (do you really need him pointed out?). Both photos are attributed to Mathew Brady, although the Hooker photo may be by Levin C. Handy.
The Wide Awake Quickstep, possibly performed on 11 September 1860 for a meeting of “The Wide Awakes,” is from Schreiber’s Albany Cornet Band, which was organized 12 June 1860. Information about the Wide Awakes is available at wikipedia.
An engraving of a Wide Awake’s 1860 rally.
A Wide Awakes website also exists for an organization that claims to be of the order of the original movement (someone can confirm or deny this accordingly). This can be found at www.wideawakes.net.
07. Introduction to “Meditation: 20 Years Ago” – 2:54
08. Meditation: 20 Years Ago – 3:07
“That tune is enough to make an E-flat cornet player dizzy.” – Jeff Stockham
This medley was arranged by George Holton Goodwin. “20 Years Ago” is reported by Ward Hill Lamon to be Lincoln’s favorite piece of music. The piece “20 Years Ago” was written by William Willing in 1856. “Ever Of Thee” was written by Foley Hall and George Linley in 1852. A link to sheet music (and a snippet of audio) can be found at the National Library of Australia website at catalogue.nla.gov.au/Record/1683158. A copy of the cover is shown below.
The quickstep version performed here is attributed to the Manchester Massachusetts Cornet Band (there also exists a Manchester New Hampshire Cornet Band if you google around. Accept no Manchester imitations! That said, there is a complete history of the Manchester New Hampshire Cornet Band from 1890 available in PDF format (as well as the usual browser-friendly format) at google books: books.google.com/books?id=5PBYAAAAMAAJ&printsec=frontcover#v=onepage&q=&f=false).
Another piece by George Holton Goodwin titled “Door Latch Quickstep” can be found at www.digitalhistory.uh.edu/audio/music2.cfm. The tune is near the bottom of the top-fifth of the website. A copy of the provided MP3 from the Library of Congress is provided locally HERE.
10. The Irish Medley: The Sprig of Shillelagh, Rakes of Mallow, and Lament of the Irish Immigrant – 2:43
The alternate name for “Lament of the Irish Immigrant” is “I’m Sitting On The Stile, Mary.” The Irish Medley is from The Squire’s Brass Band Olio. I’ve found precious little online about the music and the band, but direct you to the following few links for some additional information:
Adelina Patti 1843-1919, Spanish Opera Singer. From wikipedia.org.
From the wikipedia entry for Adelina Patti: “In 1862 she sang John Howard Payne’s Home, Sweet Home at the White House for Abraham and Mary Lincoln, who were mourning for their son Willie, who had died of typhoid. The Lincolns were moved to tears and requested an encore. This song would became associated with Adelina Patti. She performed it many times as an encore by popular request.”
It probably was in this room that singer Madame Patti came to visit with and sing for the Lincolns. She said later that “we were received by Mrs. Lincoln in one of the big parlors. The President’s wife was a handsome woman, almost regal in her deep black and expansive crinoline, only an outline of white at throat and wrists. Her manner was most gracious without a particle of reserve or stiffness. ‘My dear, it is very kind of you to come to see us,’ she said. Taking both my hands in hers and smiling in my face, she added,’I have wanted to see you; — to see the young girl who has done so much, who has set the whole world talking of her wonderful singing.’” After several songs, Madame Patti accompanied herself on the piano while singing, ‘The Last Rose of Summer.’ She realized afterwards that she had “made an awkward choice.’ Mary has “risen from her seat and was standing at a window in the back part of the room with her back toward me. I could not see her face but I knew she was weeping.” Mr. Lincoln then requested ‘Home Sweet Home.”
Historian David Rankin Barbee wrote that her accompanist “did not know the air, and Patti, who knew it, did not know the words, and had never sung them. Seeing her dilemma, ‘the President rose from his seat, went quickly to a small stand at the foot of the piano, took from it a small music book, with a vivid green color, and placed it on the piano rack, opened to the music of Home, Sweet Home. Then he returned to his seat without a word and resumed his former posture. ‘Well, I sang the song the very best I could do it,’ Patti concluded,’and when Mr. Lincoln thanked me his voice was husky and his eyes were full of tears. By that time I was so wrought up over the situation myself that I was actually blubbering when we were taking leave of the recently bereaved parents.’”
Charles Gounod in 1859, the same year as the first performance of Faust. From wikipedia.org.
For another take on the Soldier’s Chorus, I refer you to youtube:
15. Introduction to “Old Hundredth” – 4:20
16. Old Hundredth – 1:34
“Old Hundredth” refers to Psalm 100, “All People That on Earth Do Dwell,” put to music (possibly first) in 1551 in Pseaumes Octante Trois de David, from the second edition of the collection of metrical psalms in the Genevan Psalter (the music itself is attributed to French composer Loys Bourgeois).
All people that on earth do dwell,
Sing to the Lord with cheerful voice.
Him serve with fear, His praise forth tell;
Come ye before Him and rejoice.
In combination with the text from the performance, Lincoln’s Gettysburg Address is provided in its entirety below (using his aptitude for impact and brevity as a metric, Lincoln would have made one helluva blogger). I remember Carlos Moroz memorizing this for our 4th Grade English class (I had picked a section of George Washington’s Farewell Address) and thinking it was pretty good (well, it was 4th Grade).
So brief, the photographer only caught Lincoln as he sat down. From wikipedia.org.
Four score and seven years ago our fathers brought forth on this continent a new nation, conceived in Liberty, and dedicated to the proposition that all men are created equal.
Now we are engaged in a great civil war, testing whether that nation, or any nation, so conceived and so dedicated, can long endure. We are met on a great battle-field of that war. We have come to dedicate a portion of that field, as a final resting place for those who here gave their lives that that nation might live. It is altogether fitting and proper that we should do this.
But, in a larger sense, we can not dedicate…we can not consecrate…we can not hallow this ground. The brave men, living and dead, who struggled here, have consecrated it, far above our poor power to add or detract. The world will little note, nor long remember what we say here, but it can never forget what they did here. It is for us the living, rather, to be dedicated here to the unfinished work which they who fought here have thus far so nobly advanced. It is rather for us to be here dedicated to the great task remaining before us—that from these honored dead we take increased devotion to that cause for which they gave the last full measure of devotion—that we here highly resolve that these dead shall not have died in vain—that this nation, under God, shall have a new birth of freedom—and that government: of the people, by the people, for the people, shall not perish from the earth.
Quest for Sound curator Jay Allison unearthed a unique recording: the voice of William V. Rathvon, who as a nine-year-old boy, watched and listened to Abraham Lincoln deliver his address at Gettysburg in November 1863. The story was told in 1938 and recorded on a 78 r.p.m. record.
A family in Pallatine, Illinois shared this recording with us via our Quest for Sound phone line. Rathvon was a distant relative. No other Gettysburg eyewitness is known to have recorded their memories on record.
And, for even more Civil War-specific information, check out the content at Old Hundredth Press (www.oldhundredthpress.com).
17. Introduction to “Dixie’s Land” – 3:18
18. Dixie’s Land – 1:38
Yes, that “Dixie’s Land,” famous enough that it has its own wikipedia page (en.wikipedia.org/wiki/Dixie_%28song%29). According to the record, this piece was written with 48-hours notice by Daniel Decatur Emmett in September, 1859, with the first reported performance by Bryant’s Minstrels, a famed blackface minstrel troupe [the blog author shakes his head] from New York City.
The historical record reports the following about the most significant performance of this piece, requested by Lincoln upon the surrender of Lee to Grant at Appomattox.
“General Robert E. Lee surrendered to General Ulysses S. Grant on April 9, 1865. The next day, despite rain and mud there were some 3,000 people in the streets celebrating. Crowds serenaded President Lincoln throughout the day. “At length,” wrote a reporter for the Washington paper Daily National Intelligencer, “after persistent effort, the presence of Mr. Lincoln was secured. Three loud and hearty cheers were given, after which the President said:
‘FELLOW CITIZENS: I am very greatly rejoiced to find that an occasion has occurred so pleasurable that the people cannot restrain themselves. [Cheers.] I suppose that arrangements are being made for some sort of a formal demonstration, this, or perhaps, to-morrow night. [Cries of `We can't wait,' `We want it now,' &c.] If there should be such a demonstration, I, of course, will be called upon to respond, and I shall have nothing to say if you dribble it all out of me before. [Laughter and applause.] I see you have a band of music with you. [Vocies, `We have two or three.'] I propose closing up this interview by the band performing a particular tune which I will name. Before this is done, however, I wish to mention one or two little circumstances connected with it. I have always thought `Dixie’ one of the best tunes I have ever heard. Our adversaries over the way attempted to appropriate it, but I insisted yesterday that we fairly captured it. [Applause.] I presented the question to the Attorney General, and he gave it as his legal opinion that it is our lawful prize. [Laughter and applause.] I now request the band to favor me with its performance.’”
“In accordance with the request, the band struck up `Dixie,’ and at its conclusion played `Yankee Doodle,’ the President remaining at the window mean-while. The President then said: `Now give three good hearty cheers for General Grant and all under his command.’ These were given with a will, after which Mr. Lincoln requested `three more cheers for our gallant Navy,’ which request was also readily granted. The President then disappeared from the window, amid the cheers of those below. The crowd then moved back to the War Department, and loud calls were again made for Secretary Stanton.”
Less than a week later, Lincoln was dead.”
19. Introduction to “Honor To Our Soldiers” – 3:25
20. Honor To Our Soldiers – 2:35
“When I leave the stage for good, I will be the most famous man in America” – John Wilkes Booth at Taltaval’s Saloon.
The play’s most famous performance came seven years later, at Ford’s Theatre in Washington, D.C. on April 14, 1865. Halfway through Act III, Scene 2, the character Asa Trenchard (the title role), played that night by Harry Hawk, utters a line considered one of the play’s funniest:
“Don’t know the manners of good society, eh? Well, I guess I know enough to turn you inside out, old gal — you sockdologizing old man-trap…”
During the laughter that followed this line, John Wilkes Booth, a famous actor who was not in that night’s cast of Our American Cousin, fatally shot President Abraham Lincoln. Familiar with the play, he chose this moment in the hope that the sound of the audience’s laughter would mask the sound of his gunshot. He then leapt from Lincoln’s box to the stage and made his escape through the back of the theater to a horse he had left waiting in the alley.
21. Introduction to “Abraham Lincoln’s Funeral March” – 1:52
22. Abraham Lincoln’s Funeral March – 4:14
Abraham Lincoln’s Funeral March was composed by Christoph H. Bach of Milwaukee, WI. You can read a little more (and see him) at csumc.wisc.edu/exhibit/MusicTour/GAMBands.htm. There is some remarkable photography from this time, with a few selected pieces from google image searches and wikipedia.org below.
You can find pictures of some of the equipment (and generally snoop around about band stuff) at www.excelsiorcornetband.com/wst_page2.html. Damian Allis – Playing an 1850’s bass drum made by Blodgett & Bradford of Albany, NY
John Allis – Playing an 1850’s snare drum made by Edward Brown of Albany, NY
Al Thompson – Playing an 1855 o’er-the-shoulder E-flat bass saxhorn tuba made by Charles A. Zobish and Sons of NY
Loyal Mitchell – Playing an over-the-shoulder B-flat baritone horn with Berliner-style piston valves. Imported from Europe by J. Howard Foot of NY (1865-70)
Dickson Rothwell – Playing an over-the-shoulder E-flat alto horn. Imported from Europe
David Driesen – Playing an 1870 rotary valve side-action B-flat cornet made by The Boston musical instrument manufacturer Eldridge G. Wright
Lee Turner – Playing an 1868-1870 side-action E-flat rotary valve cornet made by D.C.Hall and Benjamin F. Quimbey
Jeff Stockham – Playing an 1866 (it’s on the bell) cornet made by Hall and Quimbey of Boston. We know even more about this particular instrument: “Presented by the members of the Brooklyn Cornet Band to Amos H. Bangel, leader, October 11 1866.” That is, for the record, the Brooklyn Cornet Band of Brooklyn, CA.
24. Introduction to “Battle Hymn Quickstep” – 2:29
25. Battle Hymn Quickstep – 2:06
Always end strong. The lyrics to the Battle Hymn of the Republic were written (partly in a dream) by Julia Ward Howe and put to the music of “John Brown’s Body,” who you may remember from the beginning of Ken Burn’s epic The Civil War (I had to fit Ken Burns into the post somewhere). The music for “John Brown’s Body” was originally written/collected by William Steffe in 1856 for a song containing the opening verse “Say, brothers, will you meet us / on Canaan’s happy shore?” A copy of the original first-printing of the poem from the Atlantic Monthly is provided below from wikipedia.org.
While there, McCabe and his fellow prisoners learned of Lee’s defeat at the Battle of Gettysburg. To celebrate, they sang every national song they knew, including Howe’s “Battle Hymn of the Republic.” After a few resounding choruses of “Glory, glory, hallelujah!” the guards put a stop to the singing.
Finally, it would not surprise me that several errors or misrepresentations may have made their way into my text. As I suspect at least a few heavy-duty Civil War nuts will find their way to this page, please do not hesitate to contact me with insights, comments, or lambasting. I’ll be happy to make changes and acknowledge accordingly. Huzzah!
I find it mildly amusing that a paper that went through several rather exhaustive crystallography-focused review cycles (fighting with crystallography-specific reviewers about the use of the vibrational spectroscopy to provide the more realistic view of this organic salt in the solid-state) makes headlines (well, you know) only for the vibrational spectroscopy. I certainly won’t point fingers (only browsers), but I’ve yet to see someone say the same of vibrational spectroscopists.
As a brief addition, the Raman spectrum presented on the spectroscopyNOW website does not provide quite the resolution of the original. In the interest of laying all doubts aside, a larger version of the same image is provided below.
The 293 K and 78 K Raman spectra of LAAN showing temperature-dependent peak changes (black box).
According to the article (his, not ours)…
Even if there turns out to be no ferroelectric transition in LAAN, it could still represent an unusual and intriguing structure in which both a neutral and zwitterionic L-alanine amino acid exist in the same crystal cell together with crystalline nitric acid. Such a material might help to improve the computational structural models, improve our understanding of the spectra of related materials and perhaps offer clues to designing a next-generation material that does have the elusive ferroelectric properties.
As first appeared in the November 2009 edition of the Syracuse Astronomical Society newsletter The Astronomical Chronicle (PDF).
Constellation Map generated with Starry Night Pro 6.
This month’s constellation is one of the best in the Night Sky for combining ancient tradition, mythology, modern astronomy, world history, stellar eye candy, and even modern engineering into one reasonably small bordered pen of celestial real estate. The early evening sight of the constellation Taurus the Bull in the November southeast sky at Darling Hill might appear to CNY viewers as a snow divining rod pointing to the western Great Lakes in anticipation of winter and the upcoming lake-effect snow. Taurus is a distinctive constellation and very easy to identify once its central asterism is identified. The brightest star in the constellation is almost equidistant from the easily identified Pleiades and the shoulder of the constellation Orion, the celestial hunter Taurus is running from as the sky appears to move (or, from the most commonly drawn orientation, right towards him!). While Taurus is mildly sparse in quantity when it comes to dark sky objects, it more than makes up for it in quality, hosting two of the most significant stellar sights in the Night Sky.
Like its neighbor Orion, Taurus the Bull is a very, very old constellation and has been recognized as a bull for the duration of its existence in Middle Eastern and European traditions. Earliest records of any kind place the birth of Taurus in the Copper (Chalcolithic) Age (4500 – 3500 B.C.E.), although some records support its existence even earlier. The presence of a bull and what appears to be a Pleiades-like star formation exists on a wall in the Lascaux Caves of France (see right). Although the interpretation of the Constellation set is controversial, this arrangement may date back as far as 16,500 years. Personally, I find even the thought of that kind of continuity between what we might see in the winter skies and what our ancestors also saw at night both comforting and humbling. Many of the same stand-out patterns we know today no doubt stood out immediately to them as the brightest objects in the sky marked out regular places as the Sun set, and the great distance we’ve traveled in history might be barely perceptible to an ancient astronomer going simply by the positions of stars.
Lascaux Cave bull and star pattern. From the Institute for Interdisciplinary Studies and spacetoday.org.
We begin the tour by aiming our sights at the bright eye of the bull, the star Aldebaran. This orange giant is 44 times the diameter of our own Sun and has already used its hydrogen fuel, leaving this fusion engine to now graze on a steady diet of helium. Its name is derived from the Arabic for “the follower,” often reported as in reference to its position below the Pleiades (so “following” this open cluster as we progress into winter). The other stars in Taurus are easy to see in darker skies but not otherwise noteworthy for their brightness at either naked-eye or binocular viewing magnification. Several of the bright stars closest to Aldebaran make up an asterism that a new observer might confuse with the complete constellation. The V-shaped Hyades (center of the image below and shown at right with white border) are composed of five stars, with Aldebaran the brightest tip. I’ll admit that the first time I marked out the space for Taurus, I confused this asterism (and lambda-Tau to the west) with the entire object before double-checking the size. No bull. The Hyades star closest to Aldebaran, theta-Tau, is actually a pair of pairs, although they only appear as a single bright pair in binoculars and telescopes.
The Hyades (white) and Pleiades (red). From Lynn Laux, nightskyinfo.com.
Caught within the bull pen is the Pleiades (M45, shown labeled below from a Hubble image). This Tiny Dipper is visible year-round during the daytime in parking lots and slow-moving traffic everywhere (as the object embedded within the emblem on every Subaru, the Japanese name for this asterism) and is one of the treats of winter viewing in CNY (unless VERY early morning viewing is your game or you’ve been trying to see Mars in the late Summer skies, in which case you’ve been enjoying the pre-dawn sight of M45 since August). The amount of information available on the Pleiades online and as part of space research could easily (and very likely has) fill an entire book. While the seven bright stars are identified from Greek mythology as the Seven Sisters (Sterope, Merope, Electra, Maia, Taygete, Celaeno, and Alcyone), the counting aid that comes from a pair of binoculars easily reveals nine stars. The two stars that make up the handle of this tiny dipper are the proud parents Atlas and Pleione, placed to the east of the dipper to protect their daughters from either Taurus (for being a bull) or Orion (for being a male). Given the long history of this asterism, it is perhaps not surprising that the parents decided not to stop at seven. In fact, there are over 1,000 distinct stars in the Pleiades that have been revealed as part of multiple high-resolution studies. This density of stars makes the Pleiades a unique open cluster, as there is a wealth of stars and patterns visible at virtually any magnification, from small binoculars to the largest ground-based telescopes. For my first proper viewing session, I spent one full hour simply looking at this cluster through my Nikon 12×50’s, amazed at just how little we really see of the Night Sky using the 1×7 binoculars built into our heads (and, perhaps, corrected by horn-rimmed glasses).
On the opposite side of Taurus and caught between the horns is the first of the categorized Messier objects, the Crab Nebula. M1 to its friends, this nebula is a supernova remnant with a remarkable history. As documented in both Arab and Chinese texts (Europe was just coming out its, er, Dark Ages at the time), this supernova was so bright on July 4, 1054 that it was visible during daylight hours (and, as you can guess by the date, visible without any magnification). The supernova remnant we know today as the Crab Nebula was discovered (and correlated to the original supernova) first by John Bevis in 1731, then by Charles Messier in 1758 while, as it happens, observing a comet (that Messier is known best for his catalogue of objects that were NOT comets instead of the comets he worked so diligently to discover is one of the great fun ironies of astronomy). The NASA images of the Crab Nebula reveal a dense sponge-like structure full of filaments of all sizes. The image above shows a remarkable sight – the full cycle of the pulsar at the heart of the crab that continues to magnetically drive the expansion of the nebula (in the series of frames, the pulsar lies below and to the right of a constant-brightness star).
Stepping forward several hundred years, Taurus also marks the present locations of Pioneer 10 and COSMOS 1844. Pioneer 10 is currently speeding in the direction of Aldebaran, having been successfully steered through the asteroid belt to make a series of images of Jupiter. At its current velocity, this trip to Aldebaran’s current location would take 2 million years, about the same amount of time it might take most of the world to decipher the meaning of the emblematic plaque attached to its exterior (below). Perhaps someday we’ll have to explain to the aliens how a civilization that could launch a complicated probe into space couldn’t see the multitude of planets in their own Solar System, then perhaps have to explain what happened to Pluto hat it no longer appears in our Solar System images. COSMOS 1844 is one of over 2440 satellites launched by the Soviet Union (and now Russia) since the first of the COSMOS series in 1962. At mag. 5, this satellite makes for a fun artificial viewing target (with a good map in hand).
The final sights for telescope viewers include four NGC objects. NGC 1746, 1647, and 1807 are open clusters with magnitudes between 6 and 7. NGC 1514 (below) is a mag 10 planetary nebula just at the far edge of the Taurus border that should be increasingly good viewing as Taurus works its way towards our zenith (1514 will be the closest it will get to our zenith by midnight, a perfect last-good-look before Darling Hill completely freezes over).
