TY  - JOUR
AU  - Gomez-Carrasco, S.
AU  - Müller, T.
AU  - Köppel, H.
TI  - Ab Initio Study of the VUV-Induced Multistate Photodynamics of Formaldehyde
JO  - The journal of physical chemistry  / A
VL  - 114
SN  - 1089-5639
CY  - Washington, DC
PB  - Soc.
M1  - PreJuSER-11459
SP  - 11436 - 11449
PY  - 2010
N1  - S. Gomez-Carrasco thanks the Alexander von Humboldt Foundation for financial support. The authors are indebted to H. Lischka for useful discussions and to COST ACTION D37/Working Group Photodyn for financial support.
AB  - Although formaldehyde, H₂CO, has been extensively studied there are still several issues not-well understood, specially regarding its dynamics in the VUV energy range, mainly due to the amount of nonadiabatic effects governing its dynamics. Most of the theoretical work on this molecule has focused on vertical excitation energies of Rydberg and valence states. In contrast to photodissociation processes involving the lowest-lying electronic states below 4.0 eV, there is little known about the photodynamics of the high-lying electronic states of formaldehyde (7-10 eV). One question of particular interest is why the (π, π*) electronic state is invisible experimentally even though it corresponds to a strongly dipole-allowed transition. In this work we present a coupled multisurface 2D photodynamics study of formaldehyde along the CO stretching and the symmetric HCH bending motion, using a quantum time-dependent approach. Potential energy curves along all the vibrational normal modes of formaldehyde have been computed using equation-of-motion coupled cluster including single and double excitations with a quadruply augmented basis set. In the case of the CO stretching coordinate, state-averaged complete active space self-consistent field followed by multireference configuration interaction was used for large values of this coordinate. 2D (for the CO stretching coordinate and the HCH angle) and 3D (including the out-of-plane distortion) potential energy surfaces have been computed for several Rydberg and valence states. Several conical intersections (crossings between potential energy surfaces of the same multiplicity) have been characterized and analyzed and a 2D 5 × 5 diabatic model Hamiltonian has been constructed. Based on this Hamiltonian, electronic absorption spectra, adiabatic and diabatic electronic populations and vibrational densities have been obtained and analyzed. The experimental VUV absorption spectrum in the 7-10 eV energy range is well reproduced, including the vibrational structure and the high irregularity in the regime of strong interaction between the (π, π*) electronic state and neighboring Rydberg states.
KW  - Formaldehyde: chemistry
KW  - Photochemical Processes
KW  - Quantum Theory
KW  - Spectrophotometry, Ultraviolet
KW  - Ultraviolet Rays
KW  - Formaldehyde (NLM Chemicals)
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
C6  - pmid:20931949
UR  - <Go to ISI:>//WOS:000283471900010
DO  - DOI:10.1021/jp106777z
UR  - https://juser.fz-juelich.de/record/11459
ER  -