Mixed quantum/classical theory for rotationally and vibrationally inelastic scattering of open-shell molecules and its application to the NH(X3Σ–) + He collisional system

Semenov, Alexander

doi:10.1063/1.5037164

Title: Mixed quantum/classical theory for rotationally and vibrationally inelastic scattering of open-shell molecules and its application to the NH(X³Σ^–) + He collisional system

Journal Article · Tue Jun 26 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5037164· OSTI ID:1543868

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)

We developed the mixed quantum/classical theory (MQCT) for rotationally and vibrationally inelastic scattering of a diatomic molecule in a ^2S+1Σ electronic state with a closed-shell atom. In this approach, the rotational (and vibrational) fine-structure states of the molecule are treated quantum-mechanically, whereas the relative motion of collisional partners is treated classically. This theory is benchmarked against full quantum (close-coupling) calculations for the NH(X³Σ^–) + He system. Good agreement is found in all cases, and MQCT reproduces all main features of energy dependence of the cross section, except narrow scattering resonances at very low energies. Our method recovers propensity rules that govern values of close-coupling cross sections. Particularly, MQCT correctly predicts that the magnitudes of F-conserving transitions are significantly larger than those of F-changing ones. Furthermore, this new development makes MQCT a viable candidate for obtaining fine-structure resolved rotational rate coefficients at higher temperatures and for complex polyatomic systems where the standard full quantum treatment is computationally infeasible.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1543868

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 24; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Fully Λ-doublet resolved state-to-state differential cross-sections for the inelastic scattering of NO(X) with Ar Eyles, C. J.; Brouard, M.; Chadwick, H. Physical Chemistry Chemical Physics, Vol. 14, Issue 16 https://doi.org/10.1039/c2cp23258h	journal	January 2012
Rotational quenching of H ₂ O by He: Mixed quantum/classical theory and comparison with quantum results Ivanov, Mikhail; Dubernet, Marie-Lise; Babikov, Dmitri The Journal of Chemical Physics, Vol. 140, Issue 13 https://doi.org/10.1063/1.4868715	journal	April 2014
A new, fully ab initio investigation of the NO(X 2Π)Ar system. I. Potential energy surfaces and inelastic scattering Alexander, Millard H. The Journal of Chemical Physics, Vol. 111, Issue 16 https://doi.org/10.1063/1.480066	journal	October 1999
Bound state spectroscopy of NH–He Kerenskaya, Galina; Schnupf, Udo; Heaven, Michael C. The Journal of Chemical Physics, Vol. 121, Issue 16 https://doi.org/10.1063/1.1808416	journal	January 2004
State-to-state differential cross sections for spin–multiplet-changing collisions of NO(X 2Π1/2) with argon Elioff, Michael S.; Chandler, David W. The Journal of Chemical Physics, Vol. 117, Issue 14 https://doi.org/10.1063/1.1505440	journal	October 2002
Rotational Spectroscopy of Diatomic Molecules Brown, John M.; Carrington, Alan https://doi.org/10.1017/CBO9780511814808	book	January 2003
Inelastic scattering of hydroxyl radicals with helium and argon by velocity-map imaging Sarma, Gautam; Marinakis, Sarantos; ter Meulen, J. J. Nature Chemistry, Vol. 4, Issue 12 https://doi.org/10.1038/nchem.1480	journal	October 2012
Quantum studies of inelastic collisions of O ₂ ( X ³ Σ ⁻ _g ) with He: Polarization effects and collisional propensity rules Corey, Gregory C.; Alexander, Millard H.; Schaefer, Joachim The Journal of Chemical Physics, Vol. 85, Issue 5 https://doi.org/10.1063/1.451029	journal	September 1986
Rotational analysis of the ND (0,0) band Bollmark, Per; Kopp, Ingvar; Rydh, Bo Journal of Molecular Spectroscopy, Vol. 34, Issue 3 https://doi.org/10.1016/0022-2852(70)90029-9	journal	June 1970
Resonances in rotationally inelastic scattering of OH( X ² Π) with helium and neon Gubbels, Koos B.; Ma, Qianli; Alexander, Millard H. The Journal of Chemical Physics, Vol. 136, Issue 14 https://doi.org/10.1063/1.3697816	journal	April 2012
The fully quantum state-resolved inelastic scattering of NO(X) + Ne: experiment and theory Brouard, M.; Chadwick, H.; Eyles, C. J. Molecular Physics, Vol. 111, Issue 12-13 https://doi.org/10.1080/00268976.2013.783940	journal	June 2013
Temperature dependence of the fine-structure resolved rate coefficients for collisions of O2(XΣ3g−) with He Lique, François The Journal of Chemical Physics, Vol. 132, Issue 4 https://doi.org/10.1063/1.3299283	journal	January 2010
Inelastic Scattering of He Atoms and NO(X ² Π) Molecules: The Role of Parity on the Differential Cross Section ^† Aoiz, F. J.; Verdasco, J. E.; Brouard, M. The Journal of Physical Chemistry A, Vol. 113, Issue 52 https://doi.org/10.1021/jp9043732	journal	December 2009
Collisional excitation of NH(X ³ Σ ⁻ ) by Ne: Potential energy surface, scattering calculations, and comparison with experiments Bouhafs, Nezha; Lique, François The Journal of Chemical Physics, Vol. 143, Issue 18 https://doi.org/10.1063/1.4935513	journal	November 2015
Inelastic Scattering of Identical Molecules within Framework of the Mixed Quantum/Classical Theory: Application to Rotational Excitations in H ₂ + H ₂ Semenov, Alexander; Babikov, Dmitri The Journal of Physical Chemistry A, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpca.6b04556	journal	May 2016
Mixed quantum/classical theory of rotationally and vibrationally inelastic scattering in space-fixed and body-fixed reference frames Semenov, Alexander; Babikov, Dmitri The Journal of Chemical Physics, Vol. 139, Issue 17 https://doi.org/10.1063/1.4827256	journal	November 2013
Quantum Theory of Angular Momentum Varshalovich, D. A.; Moskalev, A. N.; Khersonskii, V. K. https://doi.org/10.1142/0270	book	October 1988
Low-energy inelastic collisions of OH radicals with He atoms and $D_{2}$ molecules Kirste, Moritz; Scharfenberg, Ludwig; Kłos, Jacek Physical Review A, Vol. 82, Issue 4 https://doi.org/10.1103/physreva.82.042717	journal	October 2010
Zero-point Energy is Needed in Molecular Dynamics Calculations to Access the Saddle Point for H+HCN→H ₂ CN* and cis/trans -HCNH* on a New Potential Energy Surface Wang, Xiaohong; Bowman, Joel M. Journal of Chemical Theory and Computation, Vol. 9, Issue 2 https://doi.org/10.1021/ct301022q	journal	December 2012
Interaction of NH(XΣ−3) with He: Potential energy surface, bound states, and collisional Zeeman relaxation Cybulski, H.; Krems, R. V.; Sadeghpour, H. R. The Journal of Chemical Physics, Vol. 122, Issue 9 https://doi.org/10.1063/1.1857473	journal	March 2005
Rotationally inelastic scattering of OH by molecular hydrogen: Theory and experiment Schewe, H. Christian; Vanhaecke, Nicolas; Kłos, Jacek The Journal of Chemical Physics, Vol. 142, Issue 20 https://doi.org/10.1063/1.4921562	journal	May 2015
A new ab initio potential energy surface for the NH–He complex Ramachandran, R.; Kłos, J.; Lique, F. The Journal of Chemical Physics, Vol. 148, Issue 8 https://doi.org/10.1063/1.5023311	journal	February 2018
Molecular Excitation in the Interstellar Medium: Recent Advances in Collisional, Radiative, and Chemical Processes Roueff, Evelyne; Lique, François Chemical Reviews, Vol. 113, Issue 12 https://doi.org/10.1021/cr400145a	journal	October 2013
Temperature dependence of rotational excitation rate coefficients of OH(X2Π) in collision with He Kłos, J.; Lique, F.; Alexander, M. H. Chemical Physics Letters, Vol. 445, Issue 1-3 https://doi.org/10.1016/j.cplett.2007.07.035	journal	September 2007
An improved log derivative method for inelastic scattering Manolopoulos, D. E. The Journal of Chemical Physics, Vol. 85, Issue 11 https://doi.org/10.1063/1.451472	journal	December 1986
Selective rovibrational energy transfer: A classical trajectory study of collisional energy redistribution in methyl radical Peng, Grace S.; Parson, Robert P. Chemical Physics, Vol. 211, Issue 1-3 https://doi.org/10.1016/0301-0104(96)00206-6	journal	November 1996
State-to-state studies of ground state NH(X 3Σ−,v=0,J,N)+Ne Rinnenthal, Jan Leo; Gericke, Karl-Heinz The Journal of Chemical Physics, Vol. 113, Issue 15 https://doi.org/10.1063/1.1309523	journal	October 2000
Mixed quantum/classical calculations of total and differential elastic and rotationally inelastic scattering cross sections for light and heavy reduced masses in a broad range of collision energies Semenov, Alexander; Babikov, Dmitri The Journal of Chemical Physics, Vol. 140, Issue 4 https://doi.org/10.1063/1.4862409	journal	January 2014
Rotational excitation of the interstellar NH ₂ radical by H ₂ Bouhafs, Nezha; Lique, François; Faure, Alexandre The Journal of Chemical Physics, Vol. 146, Issue 6 https://doi.org/10.1063/1.4975324	journal	February 2017
MQCT. I. Inelastic Scattering of Two Asymmetric-Top Rotors with Application to H ₂ O + H ₂ O Semenov, Alexander; Babikov, Dmitri The Journal of Physical Chemistry A, Vol. 121, Issue 26 https://doi.org/10.1021/acs.jpca.7b03554	journal	June 2017
Statistical Theory of Collisional Energy Transfer in Molecular Collisions. trans -Stilbene Deactivation by Argon, Carbon Dioxide, and n -Heptane ^† Nilsson, Daniel; Nordholm, Sture The Journal of Physical Chemistry A, Vol. 110, Issue 9 https://doi.org/10.1021/jp055144k	journal	March 2006
Equivalence of the Ehrenfest theorem and the fluid-rotor model for mixed quantum/classical theory of collisional energy transfer Semenov, Alexander; Babikov, Dmitri The Journal of Chemical Physics, Vol. 138, Issue 16 https://doi.org/10.1063/1.4801430	journal	April 2013
Recent Advances in Development and Applications of the Mixed Quantum/Classical Theory for Inelastic Scattering Babikov, Dmitri; Semenov, Alexander The Journal of Physical Chemistry A, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpca.5b09569	journal	December 2015
Quantum initial conditions in quasi-classical trajectory calculations Bowman, Joel M.; Kuppermann, Aron; Schatz, George C. Chemical Physics Letters, Vol. 19, Issue 1 https://doi.org/10.1016/0009-2614(73)87052-6	journal	January 1973
Near-Threshold Inelastic Collisions Using Molecular Beams with a Tunable Velocity Gilijamse, J. J.; Hoekstra, S.; van de Meerakker, S. Y. T. Science, Vol. 313, Issue 5793 https://doi.org/10.1126/science.1131867	journal	September 2006
Gas-phase radical chemistry in the troposphere Monks, Paul S. Chemical Society Reviews, Vol. 34, Issue 5 https://doi.org/10.1039/b307982c	journal	January 2005
Mixed Quantum/Classical Theory for Molecule–Molecule Inelastic Scattering: Derivations of Equations and Application to N ₂ + H ₂ System Semenov, Alexander; Babikov, Dmitri The Journal of Physical Chemistry A, Vol. 119, Issue 50 https://doi.org/10.1021/acs.jpca.5b06812	journal	September 2015
State-to-State Inelastic Scattering of O ₂ with Helium Bishwakarma, Chandan Kumar; van Oevelen, George; Scheidsbach, Roy The Journal of Physical Chemistry A, Vol. 120, Issue 6 https://doi.org/10.1021/acs.jpca.6b00817	journal	February 2016
Scaling relations in the rotational excitation of NH( X ³ ∑ ⁻ ) N =0 by argon Dagdigian, Paul J. The Journal of Chemical Physics, Vol. 90, Issue 11 https://doi.org/10.1063/1.456376	journal	June 1989
Chemical kinetics in combustion systems: The specific effect of energy, collisions, and transport processes Wolfrum, J. Symposium (International) on Combustion, Vol. 20, Issue 1 https://doi.org/10.1016/s0082-0784(85)80545-2	journal	January 1985
Potential energy surfaces for the CN(X 2Σ+,A 2Π)Ar system and inelastic scattering within the A state Alexander, Millard H.; Yang, Xin; Dagdigian, Paul J. The Journal of Chemical Physics, Vol. 112, Issue 2 https://doi.org/10.1063/1.480720	journal	January 2000
State-to-state energy transfer of NH(X 3Σ−,v=0,J,N) in collisions with He and N2 Rinnenthal, Jan Leo; Gericke, Karl-Heinz The Journal of Chemical Physics, Vol. 116, Issue 22 https://doi.org/10.1063/1.1473662	journal	June 2002
Ab initio ground-state potential energy function and vibration-rotation energy levels of imidogen, NH Koput, Jacek Journal of Computational Chemistry, Vol. 36, Issue 17 https://doi.org/10.1002/jcc.23931	journal	April 2015
Discrete-Variable Representations and their Utilization Light, John C.; Carrington, Jr., Tucker Advances in Chemical Physics https://doi.org/10.1002/9780470141731.ch4	book	January 2000
Molecular Beam Collisions with a Magnetically Trapped Target Sawyer, Brian C.; Stuhl, Benjamin K.; Wang, Dajun Physical Review Letters, Vol. 101, Issue 20 https://doi.org/10.1103/physrevlett.101.203203	journal	November 2008
Collisional Energy Transfer in Unimolecular Reactions: Direct Classical Trajectories for CH ₄ ⇄ CH ₃ + H in Helium Jasper, Ahren W.; Miller, James A. The Journal of Physical Chemistry A, Vol. 113, Issue 19 https://doi.org/10.1021/jp900802f	journal	May 2009
Accurate Calculations of Rotationally Inelastic Scattering Cross Sections Using Mixed Quantum/Classical Theory Semenov, Alexander; Babikov, Dmitri The Journal of Physical Chemistry Letters, Vol. 5, Issue 2 https://doi.org/10.1021/jz402542w	journal	December 2013
Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO(2Π1/2) with He de Lange, Marc J. L.; Stolte, Steven; Taatjes, Craig A. The Journal of Chemical Physics, Vol. 121, Issue 23 https://doi.org/10.1063/1.1818123	journal	December 2004
Ro-vibrational quenching of CO ( v = 1) by He impact in a broad range of temperatures: A benchmark study using mixed quantum/classical inelastic scattering theory Semenov, Alexander; Ivanov, Mikhail; Babikov, Dmitri The Journal of Chemical Physics, Vol. 139, Issue 7 https://doi.org/10.1063/1.4818488	journal	August 2013
New ab initio potential energy surfaces for the ro-vibrational excitation of OH(X ² Π) by He Kalugina, Yulia; Lique, François; Marinakis, Sarantos Phys. Chem. Chem. Phys., Vol. 16, Issue 26 https://doi.org/10.1039/c4cp01473a	journal	January 2014
Low-temperature collisions of $NH (X^{3} Σ^{-})$ molecules with He atoms in a magnetic field: An ab initio study Krems, R. V.; Sadeghpour, H. R.; Dalgarno, A. Physical Review A, Vol. 68, Issue 5 https://doi.org/10.1103/physreva.68.051401	journal	November 2003
Mixed Quantum/Classical Approach for Description of Molecular Collisions in Astrophysical Environments Semenov, Alexander; Babikov, Dmitri The Journal of Physical Chemistry Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acs.jpclett.5b00496	journal	May 2015
Scattering of Stark-decelerated OH radicals with rare-gas atoms Scharfenberg, L.; Gubbels, K. B.; Kirste, M. The European Physical Journal D, Vol. 65, Issue 1-2 https://doi.org/10.1140/epjd/e2011-20009-4	journal	April 2011
Mixed quantum/classical theory for inelastic scattering of asymmetric-top-rotor + atom in the body-fixed reference frame and application to the H ₂ O + He system Semenov, Alexander; Dubernet, Marie-Lise; Babikov, Dmitri The Journal of Chemical Physics, Vol. 141, Issue 11 https://doi.org/10.1063/1.4895607	journal	September 2014
Investigation of steric effects in inelastic collisions of NO(X 2Π) with Ar Alexander, Millard H.; Stolte, Steven The Journal of Chemical Physics, Vol. 112, Issue 18 https://doi.org/10.1063/1.481401	journal	May 2000
Calculations of fine-structure resolved collisional rate coefficients for the NH(X3Σ−)-He system Toboła, Robert; Dumouchel, Fabien; Kłos, Jacek The Journal of Chemical Physics, Vol. 134, Issue 2 https://doi.org/10.1063/1.3524311	journal	January 2011
Fine and hyperfine excitation of NH and ND by He: On the importance of calculating rate coefficients of isotopologues Dumouchel, Fabien; Kłos, Jacek; Toboła, Robert The Journal of Chemical Physics, Vol. 137, Issue 11 https://doi.org/10.1063/1.4753423	journal	September 2012
Three sources of errors in the Ehrenfest treatment of inelastic scattering and possible ways of resolving them Semenov, Alexander; Babikov, Dmitri The Journal of Chemical Physics, Vol. 146, Issue 22 https://doi.org/10.1063/1.4985074	journal	June 2017
State-to-state inelastic scattering of Stark-decelerated OH radicals with Ar atoms Scharfenberg, Ludwig; Kłos, Jacek; Dagdigian, Paul J. Physical Chemistry Chemical Physics, Vol. 12, Issue 36 https://doi.org/10.1039/c004422a	journal	January 2010
Interference structures in the differential cross-sections for inelastic scattering of NO by Ar Eyles, C. J.; Brouard, M.; Yang, C. -H. Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1071	journal	June 2011
Rotationally inelastic scattering of NO(A ² Σ ⁺ ) + Ar: Differential cross sections and rotational angular momentum polarization Sharples, Thomas R.; Luxford, Thomas F. M.; Townsend, Dave The Journal of Chemical Physics, Vol. 143, Issue 20 https://doi.org/10.1063/1.4935962	journal	November 2015
Propensity rules in rotationally inelastic collisions of diatomic molecules in ³ Σ electronic states Alexander, Millard H.; Dagdigian, Paul J. The Journal of Chemical Physics, Vol. 79, Issue 1 https://doi.org/10.1063/1.445578	journal	July 1983
Rotational excitation of sulfur monoxide by collisions with helium at low temperature Lique, F.; Spielfiedel, A.; Dubernet, M. -L. The Journal of Chemical Physics, Vol. 123, Issue 13 https://doi.org/10.1063/1.2004994	journal	October 2005
Rotationally inelastic collisions of OH(X 2Π)+Ar. I. State-to-state cross sections van Beek, M. C.; ter Meulen, J. J.; Alexander, M. H. The Journal of Chemical Physics, Vol. 113, Issue 2 https://doi.org/10.1063/1.481839	journal	July 2000

Similar Records

Mixed quantum/classical calculations of total and differential elastic and rotationally inelastic scattering cross sections for light and heavy reduced masses in a broad range of collision energies

Journal Article · Tue Jan 28 00:00:00 EST 2014 · Journal of Chemical Physics · OSTI ID:1543868

Semenov, Alexander; Babikov, Dmitri

A new crossed beam approach to vibrationally inelastic scattering in neutral collision systems. State-to-state cross sections for He+I sup * sub 2 (. upsilon. prime =15, 25, 35) at E sub c. m. =89 meV

Journal Article · Fri Dec 15 00:00:00 EST 1989 · Journal of Chemical Physics; (USA) · OSTI ID:1543868

Krajnovich, D J; Butz, K W; Du, H; +1 more

Full dimensional Franck-Condon factors for the acetylene $\tilde{A}$ ¹ A _u —$\tilde{X}$ ¹Σ$^{+}_{g}$ transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

Journal Article · Tue Oct 07 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:1543868

Park, G. Barratt

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Physics

Title: Mixed quantum/classical theory for rotationally and vibrationally inelastic scattering of open-shell molecules and its application to the NH(X3Σ–) + He collisional system

Citation Formats

References (64)

Similar Records

Related Subjects

Title: Mixed quantum/classical theory for rotationally and vibrationally inelastic scattering of open-shell molecules and its application to the NH(X³Σ^–) + He collisional system