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000011459 0247_ $$2pmid$$apmid:20931949
000011459 0247_ $$2DOI$$a10.1021/jp106777z
000011459 0247_ $$2WOS$$aWOS:000283471900010
000011459 037__ $$aPreJuSER-11459
000011459 041__ $$aeng
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000011459 084__ $$2WoS$$aChemistry, Physical
000011459 084__ $$2WoS$$aPhysics, Atomic, Molecular & Chemical
000011459 1001_ $$0P:(DE-HGF)0$$aGomez-Carrasco, S.$$b0
000011459 245__ $$aAb Initio Study of the VUV-Induced Multistate Photodynamics of Formaldehyde
000011459 260__ $$aWashington, DC$$bSoc.$$c2010
000011459 300__ $$a11436 - 11449
000011459 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article
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000011459 440_0 $$03693$$aJournal of Physical Chemistry A$$v114$$x1089-5639$$y43
000011459 500__ $$aS. Gomez-Carrasco thanks the Alexander von Humboldt Foundation for financial support. The authors are indebted to H. Lischka for useful discussions and to COST ACTION D37/Working Group Photodyn for financial support.
000011459 520__ $$aAlthough 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.
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000011459 588__ $$aDataset connected to Web of Science, Pubmed
000011459 650_2 $$2MeSH$$aFormaldehyde: chemistry
000011459 650_2 $$2MeSH$$aPhotochemical Processes
000011459 650_2 $$2MeSH$$aQuantum Theory
000011459 650_2 $$2MeSH$$aSpectrophotometry, Ultraviolet
000011459 650_2 $$2MeSH$$aUltraviolet Rays
000011459 650_7 $$050-00-0$$2NLM Chemicals$$aFormaldehyde
000011459 650_7 $$2WoSType$$aJ
000011459 7001_ $$0P:(DE-Juel1)132204$$aMüller, T.$$b1$$uFZJ
000011459 7001_ $$0P:(DE-HGF)0$$aKöppel, H.$$b2
000011459 773__ $$0PERI:(DE-600)2006031-2$$a10.1021/jp106777z$$gVol. 114, p. 11436 - 11449$$p11436 - 11449$$q114<11436 - 11449$$tThe @journal of physical chemistry <Washington, DC> / A$$v114$$x1089-5639$$y2010
000011459 8567_ $$uhttp://dx.doi.org/10.1021/jp106777z
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000011459 9141_ $$y2010
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