Nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state: A four-dimensional quantum study

Xie, Changjian; Malbon, Christopher; Yarkony, David R.; Guo, Hua

doi:10.1063/1.4985147

Title: Nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2²A(3s) Rydberg state: A four-dimensional quantum study

Journal Article · Mon Jun 12 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4985147· OSTI ID:1474046

Xie, Changjian ^[1];

^[2];

^[1]

Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

Here, the quantum mechanical nonadiabatic photodissociation dynamics of the hydroxymethyl (CH₂OH) radical in its lowest absorption band is investigated for the first time on a set of coupled diabatic potential energy surfaces determined by accurately fitting a large set of ab initio data. In this two-state approximation, only the ground and first excited states of CH₂OH, which are coupled by conical intersections, are included. The reduced-dimensional dynamical model includes the CO stretch, the COH bend, the HCOH torsion, and the O–H dissociation coordinate. The experimentally measured hydrogen atom kinetic energy distribution is satisfactorily reproduced. The calculated product state distribution of the H₂CO(X) fragment indicates strong vibrational excitation in the CO stretching mode, resulting from the relatively large difference in the C–O bond length between the ground and excited electronic states of CH₂OH due to the photo-induced promotion of an electron from the half-occupied π*_CO antibonding orbital to a Rydberg orbital. In addition, the bimodal kinetic energy distribution is confirmed to originate from nonadiabatic transitions near the conical intersection along the O–H dissociation coordinate

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Research Organization:: Univ. of New Mexico, Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Contributing Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: SC0015997; AC02-05CH11231

OSTI ID:: 1474046

Alternate ID(s):: OSTI ID: 1363703

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 22; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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References (57)

Accessing Multiple Conical Intersections in the 3s and 3p _x Photodissociation of the Hydroxymethyl Radical Rodrigo, Chirantha P.; Zhou, Chuanchuan; Reisler, Hanna The Journal of Physical Chemistry A, Vol. 117, Issue 46 https://doi.org/10.1021/jp404552g	journal	May 2013
Accurate nonadiabatic dynamics Guo, Hua; Yarkony, David R. Physical Chemistry Chemical Physics, Vol. 18, Issue 38 https://doi.org/10.1039/c6cp05553b	journal	January 2016
Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol Xu, Xuefei; Yang, Ke R.; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 9, Issue 8 https://doi.org/10.1021/ct400447f	journal	July 2013
Non-adiabaticity: the importance of conical intersections Zhu, Xiaolei; Yarkony, David R. Molecular Physics, Vol. 114, Issue 13 https://doi.org/10.1080/00268976.2016.1170218	journal	May 2016
On the elimination of the electronic structure bottleneck in on the fly nonadiabatic dynamics for small to moderate sized (10-15 atom) molecules using fit diabatic representations based solely on ab initio electronic structure data: The photodissociation of phenol Zhu, Xiaolei; Yarkony, David R. The Journal of Chemical Physics, Vol. 144, Issue 2 https://doi.org/10.1063/1.4938236	journal	January 2016
Photodissociative spectroscopy of the hydroxymethyl radical (CH2OH) in the 3s and 3px states Feng, Lin; Huang, Xin; Reisler, Hanna The Journal of Chemical Physics, Vol. 117, Issue 10 https://doi.org/10.1063/1.1498469	journal	September 2002
An accurate and efficient scheme for propagating the time dependent Schrödinger equation Tal‐Ezer, H.; Kosloff, R. The Journal of Chemical Physics, Vol. 81, Issue 9 https://doi.org/10.1063/1.448136	journal	November 1984
Competitive C–H and O–D bond fission channels in the UV photodissociation of the deuterated hydroxymethyl radical CH2OD Feng, Lin; Demyanenko, Andrey V.; Reisler, Hanna The Journal of Chemical Physics, Vol. 120, Issue 14 https://doi.org/10.1063/1.1665880	journal	April 2004
Fitting coupled potential energy surfaces for large systems: Method and construction of a 3-state representation for phenol photodissociation in the full 33 internal degrees of freedom using multireference configuration interaction determined data Zhu, Xiaolei; Yarkony, David R. The Journal of Chemical Physics, Vol. 140, Issue 2 https://doi.org/10.1063/1.4857335	journal	January 2014
Nonadiabatic Photodissociation of the Hydroxymethyl Radical from the 2 ² A State. Surface Hopping Simulations Based on a Full Nine-Dimensional Representation of the 1,2,3 ² A Potential Energy Surfaces Coupled by Conical Intersections Malbon, Christopher L.; Yarkony, David R. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b00758	journal	February 2015
Vibronic eigenstates and the geometric phase effect in the ² E″ state of NO ₃ Eisfeld, Wolfgang; Viel, Alexandra The Journal of Chemical Physics, Vol. 146, Issue 3 https://doi.org/10.1063/1.4973983	journal	January 2017
Predissociation of the Hydroxymethyl Radical in the 3 p _z Rydberg State: Formaldehyde + Hydrogen Atom Channel ^† Conroy, D.; Aristov, V.; Feng, L. The Journal of Physical Chemistry A, Vol. 104, Issue 45 https://doi.org/10.1021/jp001357s	journal	November 2000
Photochemistry of the Water Molecule: Adiabatic versus Nonadiabatic Dynamics Yuan, Kaijun; Dixon, Richard N.; Yang, Xueming Accounts of Chemical Research, Vol. 44, Issue 5 https://doi.org/10.1021/ar100153g	journal	May 2011
Structural and thermochemical properties of the hydroxymethyl (CH2OH) radical: A high precision ab initio study Marenich, Aleksandr V.; Boggs, James E. The Journal of Chemical Physics, Vol. 119, Issue 19 https://doi.org/10.1063/1.1618736	journal	November 2003
Computational determination of the Ã state absorption spectrum of NH ₃ and of ND ₃ using a new quasi-diabatic representation of the X̃ and Ã states and full six-dimensional quantum dynamics Zhu, Xiaolei; Ma, JianYi; Yarkony, David R. The Journal of Chemical Physics, Vol. 136, Issue 23 https://doi.org/10.1063/1.4725496	journal	June 2012
On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data Malbon, Christopher L.; Zhu, Xiaolei; Guo, Hua The Journal of Chemical Physics, Vol. 145, Issue 23 https://doi.org/10.1063/1.4971369	journal	December 2016
Full-dimensional potentials and state couplings and multidimensional tunneling calculations for the photodissociation of phenol Yang, Ke R.; Xu, Xuefei; Zheng, Jingjing Chem. Sci., Vol. 5, Issue 12 https://doi.org/10.1039/c4sc01967a	journal	January 2014
A time-independent theory of photodissociation based on polynomial propagation Guo, Hua The Journal of Chemical Physics, Vol. 108, Issue 6 https://doi.org/10.1063/1.475629	journal	February 1998
Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH ₂ OH and CD ₂ OH). I. A theoretical study Kamarchik, E.; Rodrigo, C.; Bowman, J. M. The Journal of Chemical Physics, Vol. 136, Issue 8 https://doi.org/10.1063/1.3685891	journal	February 2012
Photodissociation Dynamics Schinke, Reinhard Cambridge University Press https://doi.org/10.1017/CBO9780511586453	book	January 2009
Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH ₂ OH and CD ₂ OH). II. Velocity map imaging studies Ryazanov, M.; Rodrigo, C.; Reisler, H. The Journal of Chemical Physics, Vol. 136, Issue 8 https://doi.org/10.1063/1.3685899	journal	February 2012
The Electronic Spectrum of H ₂ COH Revisited Bruna, Pablo J.; Grein, Friedrich The Journal of Physical Chemistry A, Vol. 105, Issue 37 https://doi.org/10.1021/jp012385t	journal	September 2001
Photodissociation Dynamics Butler, Laurie J.; Neumark, Daniel M. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp953518b	journal	January 1996
Quasi-diabatic representations of adiabatic potential energy surfaces coupled by conical intersections including bond breaking: A more general construction procedure and an analysis of the diabatic representation Zhu, Xiaolei; Yarkony, David R. The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4734315	journal	December 2012
The molecular Aharonov—Bohm effect in bound states Alden Mead, C. Chemical Physics, Vol. 49, Issue 1 https://doi.org/10.1016/0301-0104(80)85035-x	journal	June 1980
The semirigid vibrating rotor target model for quantum polyatomic reaction dynamics Zhang, J. Z. H. The Journal of Chemical Physics, Vol. 111, Issue 9 https://doi.org/10.1063/1.479696	journal	September 1999
Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH ₂ OH photodissociation Malbon, Christopher L.; Yarkony, David R. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4978708	journal	April 2017
Statistical and nonstatistical nonadiabatic photodissociation from the first excited state of the hydroxymethyl radical Yarkony, David R. The Journal of Chemical Physics, Vol. 122, Issue 8 https://doi.org/10.1063/1.1850892	journal	February 2005
Coupled potential energy surface for the F( ² P) + CH ₄ → HF + CH ₃ entrance channel and quantum dynamics of the CH ₄ · F ⁻ photodetachment Westermann, Till; Eisfeld, Wolfgang; Manthe, Uwe The Journal of Chemical Physics, Vol. 139, Issue 1 https://doi.org/10.1063/1.4812251	journal	July 2013
An improved quasi-diabatic representation of the 1, 2, 3 ¹ A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates Zhu, Xiaolei; Malbon, Christopher L.; Yarkony, David R. The Journal of Chemical Physics, Vol. 144, Issue 12 https://doi.org/10.1063/1.4944091	journal	March 2016
Nonadiabatic Quantum Chemistry—Past, Present, and Future Yarkony, David R. Chemical Reviews, Vol. 112, Issue 1 https://doi.org/10.1021/cr2001299	journal	November 2011
Full-Dimensional Quantum Dynamics of Vibrationally Mediated Photodissociation of NH ₃ and ND ₃ on Coupled Ab Initio Potential Energy Surfaces: Absorption Spectra and NH ₂ (Ã ² A ₁ )/NH ₂ (X̃ ² B ₁ ) Branching Ratios Ma, Jianyi; Xie, Changjian; Zhu, Xiaolei The Journal of Physical Chemistry A, Vol. 118, Issue 51 https://doi.org/10.1021/jp5057122	journal	July 2014
Interpolation of multi-sheeted multi-dimensional potential-energy surfaces via a linear optimization procedure Opalka, Daniel; Domcke, Wolfgang The Journal of Chemical Physics, Vol. 138, Issue 22 https://doi.org/10.1063/1.4808358	journal	June 2013
Interacting Rydberg and valence states in radicals and molecules: experimental and theoretical studies Reisler, Hanna; Krylov, Anna I. International Reviews in Physical Chemistry, Vol. 28, Issue 2 https://doi.org/10.1080/01442350902989170	journal	April 2009
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
πσ* excited states in molecular photochemistry Ashfold, Michael N. R.; King, Graeme A.; Murdock, Daniel Phys. Chem. Chem. Phys., Vol. 12, Issue 6 https://doi.org/10.1039/b921706a	journal	January 2010
Nonadiabatic tunneling via conical intersections and the role of the geometric phase Xie, Changjian; Yarkony, David R.; Guo, Hua Physical Review A, Vol. 95, Issue 2 https://doi.org/10.1103/physreva.95.022104	journal	February 2017
Stability, Properties, and Electronic g Tensors of the H ₂ COH Radical Bruna, Pablo J.; Grein, Friedrich The Journal of Physical Chemistry A, Vol. 102, Issue 18 https://doi.org/10.1021/jp973066y	journal	April 1998
Vibrationally Mediated Photodissociation: Exploring Excited-State Surfaces and Controlling Decomposition Pathways Crim, F. F. Annual Review of Physical Chemistry, Vol. 44, Issue 1 https://doi.org/10.1146/annurev.pc.44.100193.002145	journal	October 1993
Full-Dimensional Quantum State-to-State Nonadiabatic Dynamics for Photodissociation of Ammonia in its A -Band Xie, Changjian; Ma, Jianyi; Zhu, Xiaolei The Journal of Physical Chemistry Letters, Vol. 5, Issue 7 https://doi.org/10.1021/jz500227d	journal	March 2014
Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole Li, Shaohong L.; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 146, Issue 6 https://doi.org/10.1063/1.4975121	journal	February 2017
Imaging Studies of Excited and Dissociative States of Hydroxymethylene Produced in the Photodissociation of the Hydroxymethyl Radical Rodrigo, Chirantha P.; Sutradhar, Subhasish; Reisler, Hanna The Journal of Physical Chemistry A, Vol. 118, Issue 51 https://doi.org/10.1021/jp505108k	journal	July 2014
Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃ ²A‘(3p) ← X̃ ²A‘‘ Electronic Spectra and from ab Initio Calculations Johnson, Russell D.; Hudgens, Jeffrey W. The Journal of Physical Chemistry, Vol. 100, Issue 51 https://doi.org/10.1021/jp961399+	journal	January 1996
Photodissociation of the Hydroxymethyl Radical from the 2 ² A‘ ‘(3 p _z ) State: H ₂ CO and HCOH Products ^† Feng, Lin; Reisler, Hanna The Journal of Physical Chemistry A, Vol. 108, Issue 45 https://doi.org/10.1021/jp0479769	journal	November 2004
Toward eliminating the electronic structure bottleneck in nonadiabatic dynamics on the fly: An algorithm to fit nonlocal, quasidiabatic, coupled electronic state Hamiltonians based on ab initio electronic structure data Zhu, Xiaolei; Yarkony, David R. The Journal of Chemical Physics, Vol. 132, Issue 10 https://doi.org/10.1063/1.3324982	journal	March 2010
Photodissociation of the hydroxymethyl radical. I. The role of conical intersections in line broadening and decomposition pathways Hoffman, Brian C.; Yarkony, David R. The Journal of Chemical Physics, Vol. 116, Issue 19 https://doi.org/10.1063/1.1468882	journal	January 2002
High-Resolution Direct-Absorption Spectroscopy of Hydroxymethyl Radical in the CH Symmetric Stretching Region Roberts, Melanie A.; Sharp-Williams, Erin N.; Nesbitt, David J. The Journal of Physical Chemistry A, Vol. 117, Issue 32 https://doi.org/10.1021/jp312877k	journal	March 2013
Nonadiabatic Tunneling in Photodissociation of Phenol Xie, Changjian; Ma, Jianyi; Zhu, Xiaolei Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b03288	journal	June 2016
First principles determination of the NH ₂ /ND ₂ (Ã,X̃) branching ratios for photodissociation of NH ₃ /ND ₃ via full-dimensional quantum dynamics based on a new quasi-diabatic representation of coupled ab initio potential energy surfaces Ma, Jianyi; Zhu, Xiaolei; Guo, Hua The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4753425	journal	December 2012
Anchor Points Reactive Potential for Bond-Breaking Reactions Yang, Ke R.; Xu, Xuefei; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 10, Issue 3 https://doi.org/10.1021/ct401074s	journal	February 2014
O–D bond dissociation from the 3s state of deuterated hydroxymethyl radical (CH2OD) Feng, Lin; Demyanenko, Andrey V.; Reisler, Hanna The Journal of Chemical Physics, Vol. 118, Issue 21 https://doi.org/10.1063/1.1571526	journal	June 2003
Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling Xu, Xuefei; Zheng, Jingjing; Yang, Ke R. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja509016a	journal	November 2014
Communication: On the competition between adiabatic and nonadiabatic dynamics in vibrationally mediated ammonia photodissociation in its A band Xie, Changjian; Zhu, Xiaolei; Ma, Jianyi The Journal of Chemical Physics, Vol. 142, Issue 9 https://doi.org/10.1063/1.4913633	journal	March 2015
The Spectroscopy of Formaldehyde and Thioformaldehyde Clouthier, D. J.; Ramsay, D. A. Annual Review of Physical Chemistry, Vol. 34, Issue 1 https://doi.org/10.1146/annurev.pc.34.100183.000335	journal	October 1983
On the representation of coupled adiabatic potential energy surfaces using quasi-diabatic Hamiltonians: A distributed origins expansion approach Zhu, Xiaolei; Yarkony, David R. The Journal of Chemical Physics, Vol. 136, Issue 17 https://doi.org/10.1063/1.4704789	journal	May 2012
A new approach for the development of diabatic potential energy surfaces: Hybrid block-diagonalization and diabatization by ansatz Wittenbrink, Nils; Venghaus, Florian; Williams, David The Journal of Chemical Physics, Vol. 145, Issue 18 https://doi.org/10.1063/1.4967258	journal	November 2016
Time-dependent and time-independent wavepacket approaches to reactive scattering and photodissociation dynamics Balint-Kurti, Gabriel G. International Reviews in Physical Chemistry, Vol. 27, Issue 3 https://doi.org/10.1080/01442350802102379	journal	July 2008

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
quantum chemical dynamics
photodissociation
chemical compounds and components
chemical elements
Rydberg states
absorption band
antibonding molecular orbital
bond length
vibrational spectra
potential energy surfaces

Title: Nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state: A four-dimensional quantum study

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Title: Nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2²A(3s) Rydberg state: A four-dimensional quantum study