Carbon nanodot decorated graphitic carbon nitride: New insights into the enhanced photocatalytic water splitting from ab initio studies

Interfacing carbon nanodots (C-dots) with graphitic carbon nitride (g-C3N4) produces a metal-free system that has recently demonstrated significant enhancement of photo-catalytic performance for water splitting into hydrogen [Science, 2015, 347, 970–974]. However, the underlying photo-catalytic mechanism is not fully established. Herein, we have carried out density functional theory (DFT) calculations to study the interactions between g-C3N4 and trigonal/hexagonal shaped C-dots. We find that hybrid C-dots/g-C3N4 can form a type-II van der Waals heterojunction, leading to significant reduction of band gap. The C-dot decorated g-C3N4 enhances the separation of photogenerated electron and hole pairs and the composite's visible light response. Interestingly, the band alignment of C-dots and g-C3N4 calculated by the hybrid functional method indicates that C-dots act as a spectral sensitizer in hybrid C-dots/g-C3N4 for water splitting. Our results offer new theoretical insights into this metal-free photocatalyst for water splitting.

NMR (1H, 13C) and MO (ab initio, CNDO/2, EHT) studies on basic and N-protonated hydrazinecarbothioamide

The conformational preferences of hydrazinecarbothioamide (HCTA, H2NNHCSNH2) in its basic and N-protonated (PHCTA, H3NNNHCSNH2) forms have been studied by 1H and 13C NMR spectroscopy and by theoretical LCAO-MO methods (ab initio, CNDO/2 and EHT). The hindered rotation around the C---N bond has been investigated by a total line shape analysis for the thioamide protons and by the three MO methods. Changes in the molecular conformation and electronic structure on protonation are briefly discussed.

A comparison of the molecular orbital (ab initio, CNDO and EHT) methods applied to the conformational study of thiocarbonohydrazide in its basic and diprotonated forms

Conformational preferences of thiocarbonohydrazide (H2NNHCSNHNH2) in its basic and N,N′-diprotonated forms are examined by calculating the barrier to internal rotation around the C---N bonds, using the theoretical LCAO—MO (ab initio and semiempirical CNDO and EHT) methods. The calculated and experimental results are compared with each other and also with values for N,N′-dimethylthiourea which is isoelectronic with thiocarbonohydrazide. The suitability of these methods for studying rotational isomerism seems suspect when lone pair interactions are present.

Anomeric effect in sulfur-containing systems: An Ab-initio study

The anomeric effect in S---C---S and O---C---S systems was studied by using closed-shell Hartree-Fock theory. A comparison of the STO-3G level with the 4–31G and 6–31G* levels was performed for the O---C---O system, and the STO-3G level found adequate for study of the anomeric effect. Optimization of bond lengths and angles was conducted at the STO-3G level and limited studies were made at the 4–31G level. The nature of the torsional potential curves is compared for the O---C---O, O---C---S, and S---C---S systems. The possible reasons for the decreased anomeric effect in sulfur systems are discussed.

Application of ab initio molecular orbital calculations to the structural moieties of carbohydrates. 3

Ab initio RHF/4-31G level molecular orbital calculations have been carried out on dimethoxymethane as a model compound for the acetal moiety in methyl pyranosides. The calculations are consistent with the predictions of the anomeric effect and the exo-anomeric effect. They reproduce very successfully the differences in molecular geometry observed by x-ray and neutron diffraction of single crystals of the methyl cy-D- and methyl 0-D-pyranosides. Calculations carried out at the 6-3 1G* level for methanediol confirm the earlier calculations at the 4-31G level, with smaller energy differences between the four staggered conformations.

Ab initio molecular dynamics simulations of excited hydrogen halides and methyl halides

Using excited-state ab initio molecular dynamics simulations employing the complete-active-space self-consistent-field approach, we study the mechanism of photodissociation in terms of time evolution of structure, kinetic energy, charges and potential energy for the first excited state of hydrogen halides and methyl halides. Although the hydrogen halides and methyl halides are similar in the photodissociation mechanism, their dynamics are slightly different. The presence of the methyl group causes delay in photodissociation as compared to hydrogen halides.

Ab initio electronic structures of rhombohedral and cubic HgXO3 (X = Ti, Pb)

First-principles calculations were performed for orthorhombic HgO, rhombohedral and cubic phases of HgTiO3 (HTO) and HgPbO3 (HPO). The calculations show that in the rhombohedral phase HTO is a direct gap insulator with a gap of ~1.6 eV. The rhombohedral phase of HPO, on the other hand, shows a weak metallic character. The results provide an explanation for the electrical properties of these compounds. The cubic phases of HTO and HPO are invariably metallic in nature, thereby suggesting that for HTO the rhombohedral–cubic transition must also be accompanied by a change in the electrical state. Examination of the electronic density of states of these systems revealed no significant on-site mixing of Hg 5d and Hg 6s states in any of these materials.

Ab initio studies on proton transfer involving Schiff base and related nitrogen compounds

Proton transfer across cationic hydrogen bonds involving Schiff base, ammonia and related compounds has been studied at the 4-31G level. Proton transfer characteristics are correlated to the proton affinities of the species involved. Hydrogen bond strengths of these hydrogen bonds are correlated to the differences in the proton affinity of the donor and the acceptor. Influence of a neighbouring hydrogen bond on the proton transfer from Schiff base to ammonia and Schiff base to water is also discussed.

An ab-initio study of the proton affinity of conjugated schiff-base and related nitrogen compounds: an analysis of the triggering site of bacteriorhodopsin

The chemical groups which take part in the proton transfer reaction in bacteriorhodopsin have been studied by ab initio quantum chemical methods. The various factors such as conjugation with a linear system, electron delocalization of the guanidine type, cis-trans isomerism, geometry distortion and hydrogen bonding with charged groups can influence the properties of a given chemical group. Several systems are studied at 4-31G and STO-3G levels. Some of the Schiff-base analogues and guanidine type molecules are characterized by their molecular orbital diagrams, energy levels and the nature of charge distribution. Also, the effects of the above-mentioned factors on proton affinity are studied. It is hoped that the values thus obtained can be helpful in evaluating various structural models for proton transfer.

Ab-initio molecular orbital studies on C---H…X hydrogen bonded systemsstar

C---H…X hydrogen bonded systems are studied by the STO-3G method. The proton donor ability of carbon is analysed in terms of its hybridization states and the substituents.

Ab initio studies on the tri- and diphosphate fragments of adenosine triphosphate

Pyrophosphate prototypes such as methyl triphosphate and methyl diphosphate molecules in their different protonation states have been investigated at high levels of quantum chemical calculations. The optimized geometries, the thermochemistry of the hydrolysis and the molecular orbitals contributing to the high energy of these compounds have been analyzed. These investigations provide insights into the "high energy" character of ATP molecule. Further, the dependence of vibrational frequencies on the number of phosphate groups and the charged states has also been presented. These results can aid the interpretation of spectra obtained by experiments on complexes containing pyrophosphate prototypes.

Bond length distortions associated with torsion potentials; ab-initio studies on methanedio

The 4-31G basis set is used to study the bond length variations as functions of dihedral angels in methanediol. This study is compared with O---C---O bond angle optimization studies by Gorenstein and Kar and the possible reason for bond length shorteing in the trans---trans configuration is analysed.

Ab initio studies on the tri- and diphosphate fragments of adenosine triphosphate

Pyrophosphate prototypes such as methyl triphosphate and methyl diphosphate molecules in their different protonation states have been investigated at high levels of quantum chemical calculations. The optimized geometries, the thermochemistry of the hydrolysis and the molecular orbitals contributing to the high energy of these compounds have been analyzed. These investigations provide insights into the ``high energy'' character of ATP molecule. Further, the dependence of vibrational frequencies on the number of phosphate groups and the charged states has also been presented. These results can aid the interpretation of spectra obtained by experiments on complexes containing pyrophosphate prototypes. (c) 2005 Elsevier B.V. All rights reserved.