Examination of Potential Energy Curves of CFCl by Multi-reference Configuration Interaction Method

Abstract

We give a detailed examination of potential energy curves of the singlet and triplet states of CFCl correlated with the lowest three dissociation limits. The calculations are carried out at the internally contracted multireference configuration interaction/cc-pV(T+d)Z level with the other two geometric parameters fixed at the X state equilibrium conformation. The vertical transition energy, the oscillator strength, the main configuration and the electron transition are also investigated at the same level.

Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Exotic Molecules and Radicals

“…These values are reasonably close to the present TBEs. For CClF, the most accurate literature value is probably the MRCI+Q/triple-ζ estimate of 3.59 eV, within 0.03 eV of our current TBE. For this compound, we are also aware of three previous experimental investigations focusing on its vibronic spectra. − For CF 2 , the SCI calculations converge rapidly even with the aug -cc-pVTZ basis and yield TBEs of 5.09 and 2.77 eV for the lowest singlet and triplet transitions.…”

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

“…These values are reasonably close to the present TBEs. For CClF, the most accurate literature value is probably the MRCI+Q/triple-ζ estimate of 3.59 eV, 79 within 0.03 eV of our current TBE. For this compound, we are also aware of three previous experimental investigations focussing on its vibronic spectra.…”

Anab initiostudy on the electronic excited states and photodissociation mechanism of bromocarbene molecule

“…In recent years, based on high-resolution laser spectroscopy and high-precision quantitative calculation methods, researchers have conducted numerous studies on CXY molecules, e.g. , monohalogenated carbenes CHF 6,7 /CHCl 8,9 /CHBr 10,11 /CHI 12–14 and dihalogenated carbenes CF 2 15,16 /CCl 2 17,18 /CBr 2 19,20 /CI 2 21 /CFCl 22,23 /CFBr, 24–26 which provide valuable information on the electronic states of the triatomic halocarbenes, such as the singlet–triplet energy gap, spectroscopic constants, photodissociation dynamics and so on.…”

“…3,4 Triatomic halogenated carbenes serve as benchmarks for comparing theoretical and experimental studies, 5 and an in-depth exploration on the dynamics of the excited states can help to elucidate the microscopic mechanisms of the related photophysical and photochemical processes. In recent years, based on high-resolution laser spectroscopy and high-precision quantitative calculation methods, researchers have conducted numerous studies on CXY molecules, e.g., monohalogenated carbenes CHF 6,7 /CHCl 8,9 / CHBr 10,11 /CHI [12][13][14] 22,23 /CFBr, [24][25][26] which provide valuable information on the electronic states of the triatomic halocarbenes, such as the singlet-triplet energy gap, spectroscopic constants, photodissociation dynamics and so on.…”