Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

Alam, Todd M.; Pearce, Charles Joseph

doi:10.1007/s00894-015-2732-z

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

Journal Article · Sun Jun 28 04:00:00 EDT 2015 · Journal of Molecular Modeling

DOI:https://doi.org/10.1007/s00894-015-2732-z· OSTI ID:1235332

Alam, Todd M. ^[1]; Pearce, Charles Joseph ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

The infrared (IR) spectra of micro-hydrated Sarin•(H₂O)_n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (~1270 to 1290 cm^–1) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (~810 to 815 cm^–1) and the C-O-P vibrational modes (~995 to 1004 cm^–1) showed that the water interactions with these functional groups were minor, and that the structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. As a result, the H₂O•H₂O vibrational modes (~3450 to 3660 cm^–1) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: DTRA

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1235332

Report Number(s):: SAND--2015-1636J; 567435

Journal Information:: Journal of Molecular Modeling, Journal Name: Journal of Molecular Modeling Journal Issue: 7 Vol. 21; ISSN 1610-2940

Publisher:: Springer-VerlagCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Degradation of Adsorbed Sarin on Activated Carbons: A31P-MAS-NMR Study Kaplan, Doron; Shmueli, Liora; Nir, Ido CLEAN – Soil, Air, Water, Vol. 35, Issue 2 https://doi.org/10.1002/clen.200600008	journal	April 2007
Ab initio and ABEEM/MM fluctuating charge model studies of dimethyl phosphate anion in a microhydrated environment Wang, Fang-Fang; Zhao, Dong-Xia; Gong, Li-Dong Theoretical Chemistry Accounts, Vol. 124, Issue 1-2 https://doi.org/10.1007/s00214-009-0592-2	journal	June 2009
Ambient Volatility of DMMP Tevault, D. E.; Buchanan, J. H.; Buettner, L. C. International Journal of Thermophysics, Vol. 27, Issue 2 https://doi.org/10.1007/s10765-006-0044-3	journal	March 2006
Vibrational spectra of sarin and soman conformers Elkin, M. D.; Tatarinov, S. I.; Stepanovich, E. Yu. Journal of Applied Spectroscopy, Vol. 77, Issue 4 https://doi.org/10.1007/s10812-010-9356-y	journal	August 2010
The role of heterogeneity in the kinetics of a surface reactionI. Infrared characterization of the adsorption structures of organophosphonates and their decomposition Kuiper, A.; Vanbokhoven, J.; Medema, J. Journal of Catalysis, Vol. 43, Issue 1-3 https://doi.org/10.1016/0021-9517(76)90302-X	journal	June 1976
A comparison of the B3LYP and MP2 methods in the calculation of phosphate complexes Murashov, V. V.; Leszczynski, J. Journal of Molecular Structure: THEOCHEM, Vol. 529, Issue 1-3 https://doi.org/10.1016/S0166-1280(00)00524-8	journal	September 2000
Single crystal WO3 nanoflakes as quartz crystal microbalance sensing layer for ultrafast detection of trace sarin simulant Zhao, Yingqiang; He, Junhui; Yang, Mingqing Analytica Chimica Acta, Vol. 654, Issue 2 https://doi.org/10.1016/j.aca.2009.09.029	journal	November 2009
Effects of high relative humidity on the dynamic adsorption of dimethyl methylphosphonate (DMMP) on activated carbon Kaplan, Doron; Nir, Ido; Shmueli, Liora Carbon, Vol. 44, Issue 15 https://doi.org/10.1016/j.carbon.2006.06.036	journal	December 2006
Ab initio investigation of Sarin micro-hydration Alam, Todd M.; Pearce, Charles J.; Jenkins, Janelle E. Computational and Theoretical Chemistry, Vol. 995 https://doi.org/10.1016/j.comptc.2012.06.022	journal	September 2012
Photoassisted removal of sarin vapor in air under UV light irradiation Zuo, Guo-Min; Cheng, Zhen-Xing; Shi, Wen-Ping Journal of Photochemistry and Photobiology A: Chemistry, Vol. 188, Issue 2-3 https://doi.org/10.1016/j.jphotochem.2006.12.001	journal	May 2007
Calculated infrared spectra of nerve agents and simulants Mott, Adam J.; Rez, Peter Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 91 https://doi.org/10.1016/j.saa.2012.02.010	journal	June 2012
Nerve agent stereoisomers: analysis, isolation and toxicology Benschop, H. P.; De Jong, L. P. A. Accounts of Chemical Research, Vol. 21, Issue 10 https://doi.org/10.1021/ar00154a003	journal	October 1988
Fourier transform infrared and Raman spectra of dimethyl methylphosphonate adsorbed on montmorillonite Bowen, John M.; Powers, C. Ray.; Ratcliffe, A. E. Environmental Science & Technology, Vol. 22, Issue 10 https://doi.org/10.1021/es00175a008	journal	October 1988
Decomposition of Adsorbed VX on Activated Carbons Studied by ³¹ P MAS NMR Columbus, Ishay; Waysbort, Daniel; Shmueli, Liora Environmental Science & Technology, Vol. 40, Issue 12 https://doi.org/10.1021/es052226d	journal	June 2006
Degradation of Sulfur Mustard and Sarin over Hardened Cement Paste Tang, Hairong; Cheng, Zhenxing; Zhou, Liming Environmental Science & Technology, Vol. 43, Issue 5 https://doi.org/10.1021/es801556r	journal	March 2009
Facile Hydrolysis-Based Chemical Destruction of the Warfare Agents VX, GB, and HD by Alumina-Supported Fluoride Reagents Gershonov, E.; Columbus, I.; Zafrani, Y. The Journal of Organic Chemistry, Vol. 74, Issue 1 https://doi.org/10.1021/jo8019972	journal	January 2009
New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p) Andersson, M. P.; Uvdal, P. The Journal of Physical Chemistry A, Vol. 109, Issue 12 https://doi.org/10.1021/jp045733a	journal	March 2005
Matrix Isolation Infrared Spectroscopic and Theoretical Study of the Interaction of Water with Dimethyl Methylphosphonate Ault, Bruce S.; Balboa, Alex; Tevault, David The Journal of Physical Chemistry A, Vol. 108, Issue 46 https://doi.org/10.1021/jp046518x	journal	November 2004
An Evaluation of Harmonic Vibrational Frequency Scale Factors Merrick, Jeffrey P.; Moran, Damian; Radom, Leo The Journal of Physical Chemistry A, Vol. 111, Issue 45 https://doi.org/10.1021/jp073974n	journal	November 2007
Interactions of Phosphororganic Agents with Water and Components of Polyelectrolyte Membranes Lee, Ming-Tsung; Vishnyakov, Aleksey; Gor, Gennady Yu. The Journal of Physical Chemistry B, Vol. 115, Issue 46 https://doi.org/10.1021/jp207469h	journal	November 2011
Surface Binding of Organophosphates on Silica: Comparing Experiment and Theory Taylor, DeCarlos E.; Runge, Keith; Cory, Marshall G. The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp306713d	journal	February 2013
Infrared Spectra and Binding Energies of Chemical Warfare Nerve Agent Simulants on the Surface of Amorphous Silica Wilmsmeyer, Amanda R.; Gordon, Wesley O.; Davis, Erin Durke The Journal of Physical Chemistry C, Vol. 117, Issue 30 https://doi.org/10.1021/jp404265s	journal	July 2013
Ab Initio Studies on Organophosphorus Compounds. 5. Interactions of Dianionic Bisphosphonate Compounds with Magnesium and Calcium Räsänen, Jari P.; Pohjala, Esko; Nikander, Hannu The Journal of Physical Chemistry, Vol. 100, Issue 20 https://doi.org/10.1021/jp952858u	journal	January 1996
Harmonic Vibrational Frequencies: An Evaluation of Hartree−Fock, Møller−Plesset, Quadratic Configuration Interaction, Density Functional Theory, and Semiempirical Scale Factors Scott, Anthony P.; Radom, Leo The Journal of Physical Chemistry, Vol. 100, Issue 41 https://doi.org/10.1021/jp960976r	journal	January 1996
Ab Initio Studies on Organophosphorus Compounds. 6. ^1-5 Interactions of Dimethylphosphinic and Dimethylphosphinothioic Acid Monoanions and Methylenebisphosphonic Acid Dianion with Calcium Räsänen, Jari P.; Pohjala, Esko; Nikander, Hannu The Journal of Physical Chemistry A, Vol. 101, Issue 28 https://doi.org/10.1021/jp971213m	journal	July 1997
An Infrared Study of Adsorbed Organophosphonates on Silica: A Prefiltering Strategy for the Detection of Nerve Agents on Metal Oxide Sensors Kanan, Sofian M.; Tripp, Carl P. Langmuir, Vol. 17, Issue 7 https://doi.org/10.1021/la001624l	journal	April 2001
On the Adsorption of Dimethyl Methylphosphonate on Self-Assembled Alkanethiolate Monolayers: Influence of Humidity Bertilsson, Lars; Potje-Kamloth, Karin; Liess, Hans-Dieter Langmuir, Vol. 15, Issue 4 https://doi.org/10.1021/la980066w	journal	February 1999
Ab initio studies on organophosphorus compounds. Part 4. Intramolecular hydrogen bonding and water interactions of bisphosphonates Räsänen, Jari P.; Pohjala, Esko; Pakkanen, Tapani A. J. Chem. Soc., Perkin Trans. 2, Issue 1 https://doi.org/10.1039/P29960000039	journal	January 1996
Accuracy of the microsolvation–continuum approach in computing the pKa and the free energies of formation of phosphate species in aqueous solution Tang, Emilia; Di Tommaso, Devis; de Leeuw, Nora H. Physical Chemistry Chemical Physics, Vol. 12, Issue 41 https://doi.org/10.1039/c0cp00175a	journal	January 2010
Microsolvation of dimethylphosphate: a molecular model for the interaction of cell membranes with water Ibargüen, César; Manrique-Moreno, Marcela; Hadad, C. Z. Physical Chemistry Chemical Physics, Vol. 15, Issue 9 https://doi.org/10.1039/c2cp42778h	journal	January 2013
Adsorption competition onto activated carbon, studied by magic-angle spinning NMR Harris, Robin K.; Thompson, Timothy V.; Norman, Paul R. Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 14 https://doi.org/10.1039/ft9969202615	journal	January 1996
Micro-scale Synthesis and In-Situ Spectroscopic Characterization of Some Chemical Weapons Related Organophosphonate Compounds Durst, H. Dupont; Mays, Jeffrey R.; Ruth, Jill L. Analytical Letters, Vol. 31, Issue 8 https://doi.org/10.1080/00032719808002877	journal	June 1998
Vapor-Phase Infrared Spectral Study of Analogs of the Nerve Agent Sarin McGarvey, David J.; Stuff, John R.; Williams, Barry R. Spectroscopy Letters, Vol. 33, Issue 6 https://doi.org/10.1080/00387010009350158	journal	November 2000
The sources, fate, and toxicity of chemical warfare agent degradation products. Munro, N. B.; Talmage, S. S.; Griffin, G. D. Environmental Health Perspectives, Vol. 107, Issue 12 https://doi.org/10.1289/ehp.99107933	journal	December 1999
Organophosphorus compounds as chemical warfare agents: a review Delfino, Reinaldo T.; Ribeiro, Tatiana S.; Figueroa-Villar, José D. Journal of the Brazilian Chemical Society, Vol. 20, Issue 3 https://doi.org/10.1590/S0103-50532009000300003	journal	January 2009

Cited By (4)

Theoretical Study of the Microhydration the Chemical Warfare Agent Sulfur Mustard Emambocus, Shëyhaane A.; Rhyman, Lydia; Ramasami, Ponnadurai ACS Omega, Vol. 5, Issue 4 https://doi.org/10.1021/acsomega.9b03061	journal	January 2020
Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study Sambrook, Mark R.; Gass, Ian A.; Cragg, Peter J. Supramolecular Chemistry, Vol. 30, Issue 3 https://doi.org/10.1080/10610278.2017.1401074	journal	November 2017
Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study Sambrook, Mark R.; Gass, Ian A.; Cragg, Peter J. Taylor & Francis https://doi.org/10.6084/m9.figshare.5594281	text	January 2017
Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study Sambrook, Mark R.; Gass, Ian A.; Cragg, Peter J. Taylor & Francis https://doi.org/10.6084/m9.figshare.5594281.v1	text	January 2017

Similar Records

Vibrational spectra of chemisorbed molecular clusters: H/sub 2/O on Ru(001)

Journal Article · Tue May 15 00:00:00 EDT 1984 · J. Chem. Phys.; (United States) · OSTI ID:6899318

Ultrafast phosphate hydration dynamics in bulk H{sub 2}O

Journal Article · Sun Jun 07 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:22415889

Ab initio molecular orbital calculations on DNA radical ions. 3. Ionization potentials and ionization sites in components of the DNA sugar phosphate backbone

Journal Article · Thu Jul 29 00:00:00 EDT 1993 · Journal of Physical Chemistry; (United States) · OSTI ID:6140607

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CWA
DFT
IR spectra
ab initio
micro-hydration
sarin
solvent

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

Citation Formats

References (35)

Cited By (4)

Similar Records

Related Subjects