skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH 2OH photodissociation

Abstract

In this work, a coupled diabatic state representation, H d, of the 1, 2, 3 2A states of CH 2OH suitable for the description of the three channel, three state photodissociation process CH 2OH(1 2A) + hv → CH 2OH(2, 3 2A) → CH 2O(X, A) + H, cis-CHOH + H, trans-CHOH + H, is reported. The representation is based on electronic structure data (energies, energy gradients, and derivative couplings) obtained exclusively from multireference configuration interaction single and double excitation wave functions. Diabat shifting is employed to improve the representation’s agreement with accurate experimental energetics. A careful analysis of the numerous minima, saddle points, and conical intersection seams is reported. The computed T 0(3 2A) ~ 35 220 cm -1 is in excellent agreement with the experimental estimate of 35 053 cm -1, and the computed channel dissociation energies, D 0, for CH 2O 9453 (10 160), cis-HCOH 30 310.2 (29 923), and trans-HCOH 28 799 (28 391) cm -1 are in good accord with the measured values given parenthetically. Lastly, these accurate energetics over a wide range of nuclear configurations strongly support the ability of this H d to enable quality simulations of nonadiabatic dynamics.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465947
Alternate Identifier(s):
OSTI ID: 1497841
Grant/Contract Number:  
SC0015997; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Malbon, Christopher L., and Yarkony, David R. Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation. United States: N. p., 2017. Web. doi:10.1063/1.4978708.
Malbon, Christopher L., & Yarkony, David R. Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation. United States. doi:10.1063/1.4978708.
Malbon, Christopher L., and Yarkony, David R. Mon . "Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation". United States. doi:10.1063/1.4978708. https://www.osti.gov/servlets/purl/1465947.
@article{osti_1465947,
title = {Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation},
author = {Malbon, Christopher L. and Yarkony, David R.},
abstractNote = {In this work, a coupled diabatic state representation, Hd, of the 1, 2, 3 2A states of CH2OH suitable for the description of the three channel, three state photodissociation process CH2OH(1 2A) + hv → CH2OH(2, 3 2A) → CH2O(X, A) + H, cis-CHOH + H, trans-CHOH + H, is reported. The representation is based on electronic structure data (energies, energy gradients, and derivative couplings) obtained exclusively from multireference configuration interaction single and double excitation wave functions. Diabat shifting is employed to improve the representation’s agreement with accurate experimental energetics. A careful analysis of the numerous minima, saddle points, and conical intersection seams is reported. The computed T0(3 2A) ~ 35 220 cm-1 is in excellent agreement with the experimental estimate of 35 053 cm-1, and the computed channel dissociation energies, D0, for CH2O 9453 (10 160), cis-HCOH 30 310.2 (29 923), and trans-HCOH 28 799 (28 391) cm-1 are in good accord with the measured values given parenthetically. Lastly, these accurate energetics over a wide range of nuclear configurations strongly support the ability of this Hd to enable quality simulations of nonadiabatic dynamics.},
doi = {10.1063/1.4978708},
journal = {Journal of Chemical Physics},
number = 13,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Figures / Tables:

Table I Table I: Generic elementary functions comprising g(i).

Save / Share:

Works referenced in this record:

On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei
journal, March 1979

  • Mead, C. Alden; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 70, Issue 5
  • DOI: 10.1063/1.437734

Statistical and nonstatistical nonadiabatic photodissociation from the first excited state of the hydroxymethyl radical
journal, February 2005

  • Yarkony, David R.
  • The Journal of Chemical Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.1850892

Accessing Multiple Conical Intersections in the 3s and 3p x Photodissociation of the Hydroxymethyl Radical
journal, May 2013

  • Rodrigo, Chirantha P.; Zhou, Chuanchuan; Reisler, Hanna
  • The Journal of Physical Chemistry A, Vol. 117, Issue 46
  • DOI: 10.1021/jp404552g

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
journal, March 2016

  • Zhu, Xiaolei; Malbon, Christopher L.; Yarkony, David R.
  • The Journal of Chemical Physics, Vol. 144, Issue 12
  • DOI: 10.1063/1.4944091

Photodissociative spectroscopy of the hydroxymethyl radical (CH2OH) in the 3s and 3px states
journal, September 2002

  • Feng, Lin; Huang, Xin; Reisler, Hanna
  • The Journal of Chemical Physics, Vol. 117, Issue 10
  • DOI: 10.1063/1.1498469

Constructing diabatic representations using adiabatic and approximate diabatic data – Coping with diabolical singularities
journal, January 2016

  • Zhu, Xiaolei; Yarkony, David R.
  • The Journal of Chemical Physics, Vol. 144, Issue 4
  • DOI: 10.1063/1.4939765

Analytic evaluation of nonadiabatic coupling terms at the MR-CI level. II. Minima on the crossing seam: Formaldehyde and the photodimerization of ethylene
journal, April 2004

  • Dallos, Michal; Lischka, Hans; Shepard, Ron
  • The Journal of Chemical Physics, Vol. 120, Issue 16
  • DOI: 10.1063/1.1668631

Competitive C–H and O–D bond fission channels in the UV photodissociation of the deuterated hydroxymethyl radical CH2OD
journal, April 2004

  • Feng, Lin; Demyanenko, Andrey V.; Reisler, Hanna
  • The Journal of Chemical Physics, Vol. 120, Issue 14
  • DOI: 10.1063/1.1665880

Capture of hydroxymethylene and its fast disappearance through tunnelling
journal, June 2008

  • Schreiner, Peter R.; Reisenauer, Hans Peter; Pickard IV, Frank C.
  • Nature, Vol. 453, Issue 7197
  • DOI: 10.1038/nature07010

Photodissociation of the hydroxymethyl radical. I. The role of conical intersections in line broadening and decomposition pathways
journal, January 2002

  • Hoffman, Brian C.; Yarkony, David R.
  • The Journal of Chemical Physics, Vol. 116, Issue 19
  • DOI: 10.1063/1.1468882

Electronic Spectroscopy and Photodissociation Dynamics of the 1-Hydroxyethyl Radical CH 3 CHOH
journal, January 2008

  • Karpichev, Boris; Edwards, Laura W.; Wei, Jie
  • The Journal of Physical Chemistry A, Vol. 112, Issue 3
  • DOI: 10.1021/jp077213w

Predissociation of the Hydroxymethyl Radical in the 3 p z Rydberg State:  Formaldehyde + Hydrogen Atom Channel
journal, November 2000

  • Conroy, D.; Aristov, V.; Feng, L.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 45
  • DOI: 10.1021/jp001357s

High-Resolution Direct-Absorption Spectroscopy of Hydroxymethyl Radical in the CH Symmetric Stretching Region
journal, March 2013

  • Roberts, Melanie A.; Sharp-Williams, Erin N.; Nesbitt, David J.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 32
  • DOI: 10.1021/jp312877k

Nonadiabatic Tunneling in Photodissociation of Phenol
journal, June 2016

  • Xie, Changjian; Ma, Jianyi; Zhu, Xiaolei
  • Journal of the American Chemical Society, Vol. 138, Issue 25
  • DOI: 10.1021/jacs.6b03288

Structural and thermochemical properties of the hydroxymethyl (CH2OH) radical: A high precision ab initio study
journal, November 2003

  • Marenich, Aleksandr V.; Boggs, James E.
  • The Journal of Chemical Physics, Vol. 119, Issue 19
  • DOI: 10.1063/1.1618736

O–D bond dissociation from the 3s state of deuterated hydroxymethyl radical (CH2OD)
journal, June 2003

  • Feng, Lin; Demyanenko, Andrey V.; Reisler, Hanna
  • The Journal of Chemical Physics, Vol. 118, Issue 21
  • DOI: 10.1063/1.1571526

On the role of conical intersections and their local topography in the photodissociation of the 1-hydroxyethyl radical
journal, December 2010


Analytic evaluation of nonadiabatic coupling terms at the MR-CI level. I. Formalism
journal, April 2004

  • Lischka, Hans; Dallos, Michal; Szalay, Péter G.
  • The Journal of Chemical Physics, Vol. 120, Issue 16
  • DOI: 10.1063/1.1668615

On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data
journal, December 2016

  • Malbon, Christopher L.; Zhu, Xiaolei; Guo, Hua
  • The Journal of Chemical Physics, Vol. 145, Issue 23
  • DOI: 10.1063/1.4971369

Multiple dynamical pathways in the O([sup 1]D)+CH[sub 4] reaction: A comprehensive crossed beam study
journal, January 2000

  • Lin, J. J.; Shu, J.; Lee, Y. T.
  • The Journal of Chemical Physics, Vol. 113, Issue 13
  • DOI: 10.1063/1.1289462

Multiphoton ionization spectroscopy and vibrational analysis of a 3 p Rydberg state of the hydroxymethyl radical
journal, May 1986

  • Dulcey, Charles S.; Hudgens, Jeffrey W.
  • The Journal of Chemical Physics, Vol. 84, Issue 10
  • DOI: 10.1063/1.449935

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH 2 OH and CD 2 OH). I. A theoretical study
journal, February 2012

  • Kamarchik, E.; Rodrigo, C.; Bowman, J. M.
  • The Journal of Chemical Physics, Vol. 136, Issue 8
  • DOI: 10.1063/1.3685891

Conditions for the definition of a strictly diabatic electronic basis for molecular systems
journal, December 1982

  • Mead, C. Alden; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 77, Issue 12
  • DOI: 10.1063/1.443853

Molecular dynamics with electronic transitions
journal, July 1990

  • Tully, John C.
  • The Journal of Chemical Physics, Vol. 93, Issue 2
  • DOI: 10.1063/1.459170

The weakly exothermic rearrangement of methoxy radical (CH 3 O ) to the hydroxymethyl radical (CH 2 OH )
journal, January 1983

  • Saebo/, Svein; Radom, Leo; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 78, Issue 2
  • DOI: 10.1063/1.444785

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH 2 OH and CD 2 OH). II. Velocity map imaging studies
journal, February 2012

  • Ryazanov, M.; Rodrigo, C.; Reisler, H.
  • The Journal of Chemical Physics, Vol. 136, Issue 8
  • DOI: 10.1063/1.3685899

The symmetry groups of non-rigid molecules
journal, June 1963