Ab initio anharmonic force field and ab initio and experimental equilibrium structures of formyl chloride

Demaison, J.; Boggs, James E.; Rudolph, Heinz Dieter

doi:10.1016/j.molstruc.2003.10.035

Cited by 22 publications

(18 citation statements)

References 34 publications

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“…Table 1 gives the geomet ric parameters of the molecules in the S 0 and T 1 states, the inversion barriers in the T 1 state, and the adia batic energies of the transition T 1 ←S 0 calculated at the CCSD(T)/cc pV(T+d)Z level of theory along with the available experimental data. [6][7][8][9][10][11] The geometric parameters of all molecules in the S 0 state calculated by the CCSD(T)/cc pV(T+d)Z method agree well with the experimental data (see Table 1). The experimental data on the structures in the T 1 state were obtained only for the H 2 CO molecule, and the results of calculations at the CCSD(T)/cc pV(T+d)Z level of theory are also in good agreement with the these data.…”

Section: Resultssupporting

confidence: 58%

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

2005

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Systematic calculations of the structures of the H 2 CO, F 2 CO, Cl 2 CO, HClCO, HFCO, and FClCO molecules in the S 0 and T 1 states were performed using the B3LYP and MP2 methods with different AO basis sets and also at the CCSD(T)/cc pV(T+d)Z level of theory. The saturation of the correlation consistent sequence of basis sets cc pV(N+d)Z (N = D, T, Q, and 5) and aug cc pV(N+d)Z (N = D, T, and Q) was studied. Recommendations for choosing the calculation method are given. The relativistic corrections were estimated. The influence of the number and type of halogen atoms on the geometric parameters of the molecules in the S 0 and T 1 states and the heights of inversion barriers in the T 1 state was investigated.Key words: quantum chemical calculations, systematic basis sets, structures of molecules in excited electronic states, inversion motion, formaldehyde, halogen substituted formalde hydes.Experimental studies of vibronic spectra of carbonyl compounds demonstrated that the carbonyl fragment in particular compounds becomes nonplanar upon excita tion from the ground (S 0 ) to the lowest triplet (T 1 ) and singlet (S 1 ) electronic states due to which a large ampli tude internal motion, viz., the inversion of the nonplanar carbonyl fragment, can occur. 1 The molecules of formaldehyde (H 2 CO) and its halo gen substituted derivatives are the simplest representa tives of carbonyl compounds and serve as convenient mod els for studying the structural features of this class of mol ecules. Many of these compounds have found use in in dustry as chemicals for organic synthesis (for example, phosgene Cl 2 CO is used as the starting material in the production of dyes, polycarbonates, urea and its deriva tives, pesticides, drugs, solvents, etc.). Some of them are generated upon photolysis and oxidation of fluoro and chloro derivatives of hydrocarbons, including freons, in the troposphere and stratosphere; it is supposed that these compounds catalyze ozone decomposition. 2-5 Hence, the physical and chemical properties of these compounds are of considerable interest.Earlier, the molecules of halogen substituted formal dehydes have been studied primarily in the ground elec tronic state by vibrational spectroscopy and gas electron diffraction. 6-10 The structure of the H 2 CO molecule in the S 0 state has been investigated in depth by micro wave and rovibrational spectroscopy. 11 Analysis of the rovibronic spectra provided information 11 on the struc tures of these molecules in the S 1 and (only for formalde hyde) T 1 states. We performed theoretical study of the structures and vibrational dynamics of formaldehyde and its halogen substituted derivatives in the S 0 and T 1 states. Our investigation included two steps. In the first step, we estimated the reliability of different methods for solving the electronic Schroedinger equation. In the second step, the chosen methods were used for studying the potential energy surface (PES) in the region, where vibrational wavefunctions are localized, and solved the nuclear Schroedinger equ...

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Section: Resultssupporting

confidence: 58%

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

2005

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“…The results of CCSD calculations are mentioned sometimes for comparison and are presented in the text only. Earlier for ground state of H 2 CO [36], HClCO [6], and FClCO [9] calculations of molecular geometry on the same or even better level were published; the systematic investigation of all six molecules in S 0 and T 1 states was reported [34] at CCSD(T)/cc-pVTZ level.…”

Section: Ccsd and Ccsd(t)mentioning

confidence: 99%

“…e X ϭ Cl, Y ϭ H; exp. combined r e (bond length) and r z (valence angles) structure [6]. f X ϭ F, Y ϭ Cl; exp.…”

Section: Ccsd and Ccsd(t)mentioning

confidence: 99%

“…r(CAO) ϭ 1.342 Å, r(COCl) ϭ 1.722 Å, r(COH) ϭ 1.084 Å, Є ClCO ϭ 110.7°, and Є HCO ϭ 116.1°values obtained by combining changes of geometric parameters upon electronic excitation as predicted by CASPT2(6-5)/ cc-pVQZ and ground state structure [6] (see Table III) were used as starting, with (COH) ϭ 39.4°t aken from Ref. [3].…”

Section: Effect Of Halogen Substitutionmentioning

confidence: 99%

“…For H 2 CO [1] and Cl 2 CO [5], r e structures were determined; for HClCO, combined r e (bond length) and r z (valence angles) [6]; for F 2 CO, r 0 [7]; for HFCO, r s [8]; and for FClCO, combined microwave and electron diffraction [9] structures were obtained. Thus, one should account for the physical meaning of experimental and theoretical (r e ) parameters (see, e.g., Refs.…”

Section: Introduction Smentioning

confidence: 99%

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Molecular parameters of tetraatomic carbonyls X₂CO and XYCO (X, Y = H, F, Cl) in the ground and lowest excited electronic states, part 1: A test ofab initiomethods

Bokarev

Dolgov

Bataev

et al. 2008

Int J of Quantum Chemistry

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Computational Methods

Demaison¹,

Vogt²

2020

Lecture Notes in Chemistry

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Ab initio anharmonic force field and ab initio and experimental equilibrium structures of formyl chloride

Cited by 22 publications

References 34 publications

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

Molecular parameters of tetraatomic carbonyls X₂CO and XYCO (X, Y = H, F, Cl) in the ground and lowest excited electronic states, part 1: A test ofab initiomethods

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Ab initio anharmonic force field and ab initio and experimental equilibrium structures of formyl chloride

Cited by 22 publications

References 34 publications

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

Theoretical study of structures of the X2CO and XYCO molecules (X and Y = H, F, or Cl) in the ground and lowest excited triplet electronic states

Molecular parameters of tetraatomic carbonyls X2CO and XYCO (X, Y = H, F, Cl) in the ground and lowest excited electronic states, part 1: A test ofab initiomethods

Computational Methods

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Molecular parameters of tetraatomic carbonyls X₂CO and XYCO (X, Y = H, F, Cl) in the ground and lowest excited electronic states, part 1: A test ofab initiomethods