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Title: Reduced dimension discrete variable representation study of cis–trans isomerization in the S1 state of C2H2

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.3570823· OSTI ID:1557690
 [1];  [2];  [3];  [4];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Univ. of California at San Francisco, San Francisco, CA (United States)
  4. The Univ. of Texas at Austin, Austin, TX (United States)
+ Show Author Affiliations

Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden $$\tilde{A}$$1A2 ← $$\tilde{X}$$1Σ$$^+_g$$ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-87ER13671
OSTI ID:
1557690
Journal Information:
Journal of Chemical Physics, Vol. 134, Issue 24; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (3)

Full-dimensional quantum mechanics calculations for the spectroscopic characterization of the isomerization transition states of HOCO/DOCO systems journal January 2018
One-colour (∼220 nm) resonance-enhanced (S 1  − S 0 ) multi-photon dissociation of acetylene: probe of the C 2 A 1 Π u  −  X 1 Σ + g band by frequency-modulation spectroscopy journal February 2020
Phase-Space Approach to Solving the Time-Independent Schrödinger Equation journal August 2012

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