Formaldehyde: Electronic structure calculations for theS0andT1states

摘要

Manyhyphen;body perturbation theory (MBPT) and coupledhyphen;cluster method calculations are reported for theS0(Xthinsp;1A1) andT1(athinsp;3APrime;) electronic states of formaldehyde. The structural parameters for theS0minimum (RCH= 1.102 Aring;, RCO= 1.211 Aring;, HCH = 116.2deg;) and theT1minimum (RCH= 1.085 Aring;,RCO= 1.327 Aring;, HCH = 118deg;, rsquo;rsquo;outhyphen;ofhyphen;planersquo;rsquo; angle = 37deg; 12prime;) agree well with experimentally deduced values. Calculated heats of reaction for dissociation to radical products and molecular products agree well with literature values. The energy barriers for dissociation to molecular products and rearrangement to hydroxycarbene are presented. Vertical and adiabatic transition energies are reported forS0rarr;T1, while a vertical transition energy forS0rarr;S1is reported.