Ab initio MRD-CI study of excited states of formyl chloride HClCO and photofragmentation along Cl–C cleavage

Mühlhäuser, Max; Gruber-Stadler, Margret

doi:10.1016/j.chemphys.2007.10.026

Cited by 5 publications

(3 citation statements)

References 59 publications

(72 reference statements)

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“…[37,[40][41][42] Other Rydberg series converging to electronically excited states of HCHO þ calculated by Pablo et al [43] have been interpreted as consisting exclusively of Rydberg transitions converging to the ground state of HCHO þ with the vertical ionization potential (IP) of 10.884 eV. Mention may be made of very recent theoretical works: the photofragmentation of HCHO by Muhlhauser and Stadler [44] and the coupled multisurface 2D photodynamics study by Gomez-Carrasco et al using quantum time-dependent approach to explain the absence of (p À p Ã ) electronic state. [45] The present paper deals with photo-absorption studies in the VUV region of 5-12 eV (2000-1050 Å ) of HCHO carried out using synchrotron radiation source.…”

Section: Introductionmentioning

confidence: 98%

Photo-Absorption Studies on Formaldehyde Using Synchrotron Radiation at Indus I

Krishnakumar

Rajasekhar

Saraswathy

et al. 2012

Spectroscopy Letters

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Photo-absorption spectra of formaldehyde (HCHO) is recorded in the range of 6-11.5 eV at various pressures (<0.001-2 mbar) at an average resolution of 1.2 Å using Photophysics beam line at the 450 MeV Indus-1 synchrotron radiation facilities at RRCAT Indore, India. The spectrum is found to consist exclusively of n ! Rydberg transitions converging to the ground state of HCHO þ . The highest identified Rydberg states, observed up to the first ionization limit of HCHO, correspond to 7s, 11p, 9d, and 12f orbitals. Analyzed electronic spectrum along with the intensities and quantum defects are presented. To interpret the observed weak valence transitions instead of strong valence transitions, a theoretical study of Rydberg and valence electronic states of HCHO is performed in the framework of single configuration interaction (CIS) and time-dependent density functional theory (TDDFT) using different basis sets. Electronic transition energies of high-lying singlet and triplet valence states as calculated using TDDFT (B3LYP) level of theory are found to give fairly-good agreement with the experimental data.

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Section: Introductionmentioning

confidence: 98%

Photo-Absorption Studies on Formaldehyde Using Synchrotron Radiation at Indus I

Krishnakumar

Rajasekhar

Saraswathy

et al. 2012

Spectroscopy Letters

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“…The first transition at 4.951 eV is an π * CO ← n O transition, which is optically dark, where π* orbital is localized on the carbonyl with minor diffuse character on Cl ( Figure 5 & Table 3). EOM-CCSD predicts the transition into the first excited state, 1 1 A , to be 4.951 eV, which is 0.089 eV lower than the result computed with MRD-CI+Q/cc-pVDZ+spd, 5.04 eV 87 . The EOM-CCSD energy, however, is closer to the gas phase experimental measurement at 4.86 eV 88 .…”

Section: Formyl Chloridementioning

confidence: 58%

Highly-excited state properties of cumulenone chlorides in the vacuum-ultraviolet

Nguyen

Peters

Fortenberry

2020

Phys. Chem. Chem. Phys.

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Section: Formyl Chloridementioning

confidence: 58%

Highly-Excited State Properties of Cumulenone Chlorides in the Vacuum-Ultraviolet

Nguyen¹,

Peters²,

Fortenberry³

2020

Preprint

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Recent observations of chloromethane in interstellar environments suggest that other organohalogens, which are known to be critically important in Earth s atmosphere, may also be of significance beyond our own terrestrial veil. This raises the question of how such molecules behave under extreme conditions such as when exposed to vacuum ultraviolet (VUV) radiation. VUV photons promote molecules to highly excited states that fragment in non-statistical patterns controlled by the initial femtosecond dynamics. A detailed understanding of VUV-driven photochemistry in complex organic molecules that consist of more than one functional group is a particularly challenging task. This quantum chemical analysis reports the electronic states and ionization potentials up to the VUV range (6 -11 eV) of the chlorine-substituted cumulenone series molecules. The valence and Rydberg properties of lone-pair terminated, π-conjugated systems are explored for their potential resonance with lone pairs from elsewhere in the system. The carbon chain elongation within the family ClHC n O, where n=1-4, influences the electronic excitations, associated wavefunctions, and ionization potentials of the molecules. The predicted geometries and ionization potentials are in good agreement with the available experimental photoelectron spectra for formyl chloride and chloroketene, n=1-2. Furthermore, comparison between the regular cumulenone species and the corresponding chlorinated derivatives exhibit similar behaviors especially for n=3, where the allene backbone in propadienone chloride is severely bent. Most notably for the excited states is that the Rydberg character becomes more dominant as the energy increases, with some retaining valence characters.

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Ab initio MRD-CI study of excited states of formyl chloride HClCO and photofragmentation along Cl–C cleavage

Cited by 5 publications

References 59 publications

Photo-Absorption Studies on Formaldehyde Using Synchrotron Radiation at Indus I

Photo-Absorption Studies on Formaldehyde Using Synchrotron Radiation at Indus I

Highly-excited state properties of cumulenone chlorides in the vacuum-ultraviolet

Highly-Excited State Properties of Cumulenone Chlorides in the Vacuum-Ultraviolet

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