Ab initio quantum chemical study of electron transfer in carboranes

Pati, Ranjit; Pineda, Andrew C.; Pandey, Ravindra; Karna, Shashi P.

doi:10.1016/j.cplett.2005.03.039

Cited by 16 publications

(15 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…␤-Carotene n ϭ 11 n ϭ 9 n ϭ 7 n ϭ 5 n ϭ 3 n ϭ 1 [9,26], where the magnitude of V DA obtained from the KT approach were slightly underestimated with respect to its MH counterparts. This lends confidence in our use of the KT approach in the present study to investigate the length-dependence of V DA of polyene oligomers.…”

Section: Bond Lengths (å)mentioning

confidence: 79%

“…The simplicity and relatively less computational demands associated with the KT approach have made it an attractive choice for investigating ET properties of complex organic and biological systems [3,4-6,9,20,24 -26]. Previous studies have shown [7,[23][24][25][26] that the accuracy of the V DA calculated by KT approach is comparable to those obtained from more rigorous techniques, such as the Marcus-Hush (MH) twostate model [21,22]. In order to further assess the accuracy of V DA for linear -electron chain molecules obtained with the use of the KT approach, we calculated the coupling matrix element for 1,3-trans-butadiene using Eq.…”

Section: Theory and Calculationsmentioning

confidence: 99%

See 1 more Smart Citation

Length‐dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study

Mallick

Karna

et al. 2009

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The electron transfer (ET) properties of -electron conjugated quasione-dimensional molecular wires, consisting of polyene, [ϾCACϽ] n (n ϭ 1-11), including ␤-carotene, is investigated using ab initio molecular orbital theory within Koopmans theorem (KT) approach. The ET coupling matrix element, V DA , for 1,3-transbutadiene molecule calculated with the KT approach shows excellent agreement with the corresponding results obtained with two-state model. The calculated values of V DA for the polyene oligomers exhibit exponential decrease in magnitude with increasing length of the wire. However, the decay curve exhibits three different regimes. The magnitude of the decay constant, ␤, decreases with the increase in length of the wire. A highly delocalized -electron cloud in the polyene chain appears to facilitate retention of the electronic coupling at large separations between the donor and acceptor centers.

show abstract

Section: Bond Lengths (å)mentioning

confidence: 79%

Section: Theory and Calculationsmentioning

confidence: 99%

Length‐dependence of electron transfer coupling matrix in polyene wires: Ab initio molecular orbital theory study

Mallick

Karna

et al. 2009

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…molecules bridged through carborane, stability, second-order NLO property, DFT Carborane, an important species of borane derivatives, obtained by replacing BH or BH -group with C or CH, has attracted considerable interest [1][2][3][4] due to its representative structure and special bond. Currently, carborane has been applied actively to different fields [5] : potential applications in medicinal drug design as hydrophobic pharmacophores [6] , antisense agents [7] , and boron carriers for boron neutron capture therapy (BNCT) [8][9][10] , and as molecular probes for molecular medical diagnostics [11] ; numerous industrial applications and its wide spread uses in synthetic chemistry [12] . Recently, the application of carborane derivatives as source compounds of thin film materials has achieved a measure of success.…”

mentioning

confidence: 99%

Structure and second-order NLO property of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7)

et al. 2007

View full text Add to dashboard Cite

Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are influenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability.One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.molecules bridged through carborane, stability, second-order NLO property, DFT Carborane, an important species of borane derivatives, obtained by replacing BH or BH -group with C or CH, has attracted considerable interest [1][2][3][4] due to its representative structure and special bond. Currently, carborane has been applied actively to different fields [5] : potential applications in medicinal drug design as hydrophobic pharmacophores [6] , antisense agents [7] , and boron carriers for boron neutron capture therapy (BNCT) [8][9][10] , and as molecular probes for molecular medical diagnostics [11] ; numerous industrial applications and its wide spread uses in synthetic chemistry [12] . Recently, the application of carborane derivatives as source compounds of thin film materials has achieved a measure of success. At the same time, with the development of nonlinear optical (NLO) study and the prospect of NLO material application, carborane derivatives as NLO material have received more attention. Due to their rigid cage structure and better thermodynamic stability, Allis et al. [13,14] designed a series of molecules linking icosahedral carborane polyhedra as bridge, employed semiempirical methods to optimize the structures and calculated their second-order NLO properties. Compared with the bridged molecule of typical conjugated group, it is found that the better activity can be obtained using icosahedral carborane polyhedra as bridge. In this paper, the model molecules using n-vertex bis-substituted carborane (n=5, 6, 7) as bridge are designed [15] . Accordingly, their structures and NLO properties are calculated. Moreover, the contributions of the bridged groups are investigated in further study.

show abstract

“…These important classes of boron-rich structures have been explored as boron carriers in boron-neutron-capture therapy and as molecular probes in medical diagnostics [20][21][22] . Researchers have also studied electron transfer properties of 10-, and 12-vertex carborane structures for their possible application in electronics 23 . Despite their rich chemistry, these inorganic cage structures have never been thought of to be large enough for encapsulating a dopant atom.…”

mentioning

confidence: 99%