Molecular Reactivity in the Ground and Excited Electronic States through Density-Dependent Local and Global Reactivity Parameters

Abstract

Molecular hardness values have been calculated for a few selected diatomics,viz., H2, HF, N2, BF, CO, and F2 in their ground and first excited electronic configurations using 4-31G double ζ type basis functions. The excited electronic configurations are so chosen that they happen to have the lowest energy for a particular symmetry, keeping in mind the validity of the excited state density functional theory for such systems. It is observed for all the molecules studied that hardness values decrease with electronic excitation. Surface plots of different local quantities like the charge density, the laplacian of the charge density, the quantum potential, the molecular electrostatic potential, and the Fukui function reveal an increase in the molecular reactivity with excitation.

Ground and excited state similarity studies by means of Fukui and dual-descriptor matrices

“…The above mentioned descriptors, formulated by means of their corresponding functions, have successfully been applied to implement studies on reactivity and other properties in the ground electronic states and in some excited ones as well as on the relationships between them [13][14][15][16][17][18]. In fact, Ref.…”

Time-dependent density functional theory as a thermodynamics

“…Recently there has been a growing interest in excited-state chemical properties [26][27][28][29]. It is our hope that the present approach might help studying chemical reactivity of excited states and the balance equations derived here will be useful for studying the time dependence of chemical bonding properties.…”

Adsorption of Microporous Silica Material (mcm-41) on Graphene Sheet as a Nano-Carrier

“…The geometries of M41, G, M41G were carried out by the Becks hybrid tree-parameter exchange functional and the non-correlation functional of Lee, Yang, and Parr (B3LYP) and M05-2X method 122 with the 6-31G * and 6-31G * * basis set of theory. 123 The calculated magnetic shielding tensor ( , ppm), shielding asymmetry and the deviation have calculated for 29 Si and 17 O nuclei in the active site of MCM-41 and for 13 C, 1 H atoms of the graphite system in gas phase at 1.8 Å, 2 Å, and 2.3 Å, which are presented in Table III Table I for three distances at two-basis set, respectively.…”

“…The second-order Fock matrix has performed to evaluate the donor-acceptor interaction in the NBO analysis. [120][121][122] The interactions result in a loss of occupancy from the localized NBO of the idealized Lewis structure into an empty non-Lewis orbital. For each donor i and acceptor j , the stabilization energy E 2 associated with the delocalization i −j can estimated as…”