Unimolecular processes in weakly bound complexes: correlated product state distributions

1995 ◽  
Vol 102 ◽  
pp. 323 ◽  
Author(s):  
L. Oudejans ◽  
R. E. Miller ◽  
W. L. Hase
Keyword(s):  
Product State ◽  
Weakly Bound ◽  
Weakly Bound Complexes

scholarly journals Modelling excited states of weakly bound complexes with density functional theory

2014 ◽  
Vol 16 (28) ◽  
pp. 14455-14462 ◽  
Author(s):  
Edward A. Briggs ◽  
Nicholas A. Besley
Keyword(s):  
Density Functional Theory ◽  
Excited States ◽  
Density Functional ◽  
Rydberg State ◽  
Dispersion Correction ◽  
Weakly Bound ◽  
Functional Theory ◽  
Weakly Bound Complexes

Different dispersion correction parameters are required to describe the interaction when the molecule is in an excited Rydberg state.

The structure and harmonic vibrational frequencies of the weakly bound complexes formed by HF with CO, CO2 and N2O

1988 ◽  
Vol 74 (5) ◽  
pp. 415-428 ◽  
Author(s):  
Ian L. Alberts ◽  
Nicholas C. Handy ◽  
Emmanuel D. Simandiras
Keyword(s):  
Vibrational Frequencies ◽  
Weakly Bound ◽  
Weakly Bound Complexes

Density functional theory (DFT) calculations on the structures and stabilities of [CnO2n+1]2– and [CnO2n+1]X2 polycarbonates containing chainlike (CO2)n units (n = 2–6; X = H or Li)

2011 ◽  
Vol 89 (6) ◽  
pp. 671-687 ◽  
Author(s):  
Pablo J. Bruna ◽  
Friedrich Grein ◽  
Jack Passmore
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Ion Pairs ◽  
Dicarboxylic Acids ◽  
Polarizable Continuum Model ◽  
Weakly Bound ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Weakly Bound Complexes

The structures and stabilities of chainlike (CO2)n (n = 2–6) polycarbonates, where adjacent C atoms are linked by C–O–C bonds, were investigated at the density functional theory (DFT) level (B3PW91/6–311G(2d,p)), including dicarboxylic dianions, [CnO2n+1]2–, and the corresponding acids, [CnO2n+1]H2, and Li salts, [CnO2n+1]Li2. At equilibrium, the most stable systems have Cs, C2, or C2v symmetries. In the gas phase, these dianions are generally metastable with respect to spontaneous ejection of one electron, yet in the presence of counterions they become stabilized, for example, as [CnO2n+1]2–(Li+)2 ion pairs. [CnO2n+1]2– linkages are also stabilized as dicarboxylic acids, [CnO2n+1]H2; we find the latter to have equilibrium conformations of higher symmetry than previously reported in the literature. To the best of our knowledge, none of the [CnO2n+1]X2 (X = Li or H) compounds with n ≥ 2 have been reported in the experimental literature (albeit, the alkyl esters C2O5R2 and C3O7R2 are commercially available). All CO bonds in C2O5X2 to C6O13X2 have single- to double-bond character (≈140–118 pm), indicating that the [CnO2n+1] moieties are held together by strong chemical forces (in contrast to the weakly bound complexes (CO2)n and (CO2)n–, n > 1). Vibrational frequencies were calculated to ensure all conformations were true minima. The IR and Raman intensities show that the high intensity C=O stretching modes (1750 ± 100 cm–1) will help in the spectral characterization of these compounds. Solvation calculations using the polarizable continuum model (PCM) find that C2O52– can be formed via CO32– + CO2 as well as CO3–[Formula: see text], each reaction having ΔG298 < 0 in practically all solvents. This result confirms the experimentally observed large solubility of CO2(g) in molten carbonates, CO3M2 (M = Li, Na, or K). In contrast, starting with n = 2, the reactions [CnO2n+1]2– + CO2 do not proceed spontaneously in any solvent (ΔG298 > 0).

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