AJP	ISSN : 0971 – 3093 Vol 24, No. 5, May, 2015

ICOPVS-2014

Jim likes to talk about his starting off from humble beginnings: all the stories of his “down-home” country living, his family, his boyhood. Who way back then would have ever imagined that instead of going to work on the railroad, he would manage to go to college at Washington & Jefferson College? That there he would discover a love greater than what he had for history, that he would discover his lifelong passion: spectroscopy?

A question of mentors, a question of chance, a question of character, a question of will and determination? Or some combination of all these things. In any case, from his small beginnings, Jim continued on to Princeton University and then on to the renowned MIT where he earned his PhD in physical chemistry!

That was way back in 1958. Over all the years since then, Jim has grown as a scientist and as a person. His research laboratories which he has directed at the University of South Carolina, and at the University of Missouri-Kansas City have watched him rise to become one of the most distinguished chemists in the global scientific community. And throughout the years, he has never forgotten his own humble beginnings; for, every PhD student, every Post doc has been treated like one of his family, being helped to adapt to research, to the local world of research, to the outside world of research. Thanks to the very close alliance he has with his wife, in his 50 years of teaching, he has supervised more than 100 doctoral students and authored over 1,000 academic refereed journal articles on the subject of vibrational and rotational spectroscopy.

Jim Durig has also participated in conferences and given lectures on his scientific expertise in countries throughout the world, on nearly all the continents! I first met Jim over 40 years ago at one of the spectroscopic conferences. And some 40 years later, our paths crossed once again at ICOPVS-2014, jointly organized by Prof Vinod Rastogi and Prof Hubert Joe, in Trivandram India, where as an invited plenary speaker, he managed to charm the audience with his now-famous mix of down-home humor and rigorous scientific calculations. We have never worked in the same fields, but I have always had a great respect for his scientific work, on his sense of duty, on his organization and energy, which have enabled him to be editor of leading journals on spectroscopy, while still teaching classes, giving talks at meetings and directing the thesis work for large numbers of students.

I also have a great respect, and affection, for Jim, as a human being. I congratulate him, and his wife as well, for these many years of accumulated successes. I am certain that Jim will continue to have a finger in the organization of a journal and/or of a conference, an eye on a spectrum, an ear open for a rising student.

 

Sylvia Turrell

June 24, 2015

Member, Editorial Board of Asian J Phys/Asian Chem Letters

---

Vol. 24, No 5 (2015) 613-634

Structural and vibrational studies of some pesticides: 2-chlorophenol,2,4,6-trichlorophenol and pentachlorophenol

 

V Dixit and R A Yadav*
Spectroscopy Laboratory, Department of Physics,
Banaras Hindu University, Varanasi -221 005, India
Dedicated to Prof J R Durig

---

Structural and vibrational investigations of fungicide molecules, namely, 2-chlorophenol (2-CP), 2,4,6-trichlorophenol (TCP) and 2,3,4,5,6-pentachlorophenol (PCP) have been carried out using the DFT (B3LYP) method employing the 6-311++G** basis set available with Gaussian-09 software for the optimized structure of the most stable conformers, if any. The vibrational assignments of the observed IR and Raman bands have been proposed in the light of the results of the DFT computations and the PEDs computed using GAR2PED software. The optimized geometrical structures have overall symmetry as Cs for all the molecules. © Anita Publications. All rights reserved.
Keywords: Pesticides, Chlorophenols, Molucular structures, Quantum chemical calculations, Potential energy distributions.

Total Refs : 36

Structural and vibrational studies of some pesticides…pdf

---

 Vol. 24, No 5 (2015) 635-656

Experimental and quantum chemical investigations on vibrational and molecular structural characteristics of vitamin B7: Biotin Molecule

 

Mayuri Srivastava^a, N P Singh^b, Astha Yadav^a and R A Yadav^a
aDepartment of Physics, Banaras Hindu University, Varanasi- 221 005, India.
^bDepartment of Physics, UP (PG) Autonomous College, Varanasi- 221 002, India

---

Experimental and theoretical investigations on the  structural and the vibrational characteristics of biotin (vitamin B7) are presented. The molecular structure and vibrational frequencies were obtained using the DFT/B3LYP calculations employing the 6-311++G** basis set available with the Gaussian 09 software. The computed spectra are compared with FTIR and FT-Raman spectra recorded in the regions 400–4000 and 100–4000 cm-1, respectively. Optimized geometrical parameters suggest that the overall symmetry of the molecule is C1. The molecule is found to possess twelve conformations. Conformational analysis was carried out to obtain the most stable configuration of the molecule. In order to assign the observed IR and Raman frequencies the potential energy distributions (PEDs) have also been computed using GAR2PED software. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping the electron density isosurface with molecular electrostatic potential (MEP) surfaces. The HOMO and LUMO were also computed and  natural bond orbital (NBO) analysis was performed. © Anita Publications. All rights reserved.
Keywords: Biotin molecule, FTIR spectra, Raman spectra, DFT, PEDs, HOMO-LUMO and MEP.

Total Refs : 53

Experimental and quantum chemical investigations on vibrational and molecular.pdf

---

 Vol. 24, No 5 (2015) 657-674

Theoretical investigation of vibrational characteristics and conducting properties of building blocks of organic conductors: TSF, TTF and their cations

 

Poonam Rani, Omkant Jha and R.A. Yadav*

Laser and Spectroscopy Laboratory Department of Physics, Banaras Hindu University, Varanasi-221005, India

---

Molecular geometries, vibrational spectra along with  IR and Raman intensities and depolarization ratios of the Raman lines of the building blocks [Tetrathiafulvalene (TTF), Tetraselenafulvalene (TSF)] of organic conductors along with their cations were investigated at the B3LYP/ 6-311++G(d,p) level (Gaussian 09 package). The calculated IR and Raman bands have been assigned to different normal modes on the basis of the calculated potential energy distributions (PEDs) and form of the normal mode with the help of Gauss View. Charge transfer occurring in the molecule has been shown by the calculated value of HOMO-LUMO energies. In order to elucidate the transfer of electrons, the vibronic coupling coefficients for the TSF → TSF+ and TTF → TTF+ transitions have been computed. Involvement of vibrational modes in conduction of molecules has been studied. The vibrational modes ν(ring) and ν (C=C) under the species a1 contribute considerably to vibronic coupling. Large vibronic coupling constants of these modes show that removal of an electron to TSF and TTF is much easier under the influence of above mentioned vibrational modes. © Anita Publications. All rights reserved.
Keywords: Molecular conductor, DFT, PEDs, HOMO-LUMO, vibronic coupling

Total Refs : 44

Theoretical investigation of vibrational characteristics and conducting properties of….pdf

---

 Vol. 24, No 5 (2015) 675-689

AB initio investigation on molecular behaviour of building blocks of organic superconductors :
4,5-ethylenedithio-1,3-dithiole-2-thione and 4,5-ethylenedithio-1,3-dithiole-2-one

 

P Rani and R A Yadav*
Spectroscopy Laboratory, Department of Physics,

Banaras Hindu University, Varanasi -221 005, India
Dedicated to Prof J R Durig

---

Molecular behaviour of the building blocks of organic superconductors namely, {4,5-Ethylenedithio-1,3-dithiole-2-thione (EDT-DTT), 4,5-ethylenedithio-1,3-dithiole-2-one (EDT-DTO)} and their cations and anion using density functional theory method B3LYP  employing the 6-311++G** basis set. The effect of addition and removal of electron on the molecular geometries, frontier MOs, ionization potential, electron affinity and other electronic properties have been investigated. The calculated frontier MO energies suggest that charge transfer occurs within the molecules. Electrical properties such as dipole moment, mean polarizability, polarizability anisotropy and first hyperpolarizability have been determined. The present calculations suggest that addition of an electron in the EDT-DTT molecule involves larger geometry modifications as compared to the removal of an electron from it, which results in the chair-like conformation. Our results indicate that EDT-DTT has better charge transfer properties as compared to EDT-DTO and EDT-DTT is a better hole transporter as compared to the electron transporter. © Anita Publications. All rights reserved.
Keywords: organic superconductors, charge transfer properties, frontier molecular orbitals, electron-molecular vibration couplings

Total refs : 54

AB initio investigation on molecular behaviour of building blocks of.pdf

---

 Vol. 24, No 5 (2015) 691-702

NLO and charge transfer properties of naphthalene acetic acid adsorbed on silver

 

Rekha T N, U Reeta Felscia and Beulah J M Rajkumar
PG & Research Department of Physics, Lady Doak College, Madurai – 625 002, India

Dedicated to Prof J R Durig

---

Nonlinear optical and charge transfer properties of naphthalene acetic acid (NAA) on silver are investigated based on DFT methods. Natural population analysis (NPA) confirms the charge transfers from silver to NAA. Natural bond orbital (NBO) analysis illustrates the orbital overlapping between silver and NAA indicating charge transfers consequently with the process of adsorption. Theoretically simulated absorption spectrum has a surface plasmon resonance peak around 498 nm with major contributions arising from the charge transfers from HOMO-2 to LUMO and HOMO-1 to LUMO excitations. Chemically reactive sites were identified through Fukui functions. Localization of electron density arising from redistribution of electrostatic potential and the reduced bandgap of NAA after adsorption on silver suggests its utility in the design of organic semiconducting devices. Enhancement in dipole moment, polarizability and hyperpolarizability of NAA after adsorption on silver indicates its potential in the design of novel NLO materials. © Anita Publications. All rights reserved.
Keywords: Naphthalene acetic acid, Silver nanoparticles, Fukui Functions, NBO analysis, NLO materials

Total Refs : 38

---

 Vol. 24, No 5 (2015) 703-711

A study of vibrational spectra of zwitterionic 3-Aminobutanoic acid, as supported by density functional calculations

 

Jayashree Yenagi*, Shashikala Yalagi, and J Tonannavar
Vibrational Spectroscopy Group, Department of Physics
Karnatak University, Pavate Nagar, Dharwad -580 003, India
Dedicated to Prof J R Durig

---

Zwitterionic form of solid unnatural amino acid, 3-Aminobutanoic acid, is apparent both as an individual species and in dimeric form as the vibrational modes in the observed IR and Raman spectra near 3030 – 2990 cm^–1 and 1685 – 1540 cm^–1. The IR region 3500 – 2000 cm^–1marked by an intense broad band with sub-band structure, as is true of many amino acids, is presumably due to hydrogen bonding. A weak Raman band at 1682 cm^–1, two very intense doublet at 1663, 1634 cm^–1, two more intense doublet at 1557, 1552 cm^–1are assigned to the carbonyl (C=O) stretching, asymmetric/symmetric stretching of carboxylate (CO2¯ ) and asymmetric/symmetric deformation vibrations of ammonium (NH3+). The assignments are consistent with the assumption that the solid sample of 3-Aminobutanoic acid is composed of both zwitterionic and its hydrogen bonded dimer species. Further, DFT calculations at B3LYP/6-31G* level of theory for the neutral free 3-Aminobutanoic acid that has produced a vibration spectrum at variance with the measured modes due to carboxylic acid (–COOH) and amine (–NH2) moieties but it indirectly supports analysis. A linkage between NH2 group and H atom from COOH as shown in the optimized geometry is a signature of the tendency of the molecule to form zwitterionic species. © Anita Publications. All rights reserved.

Keywords: Zwitterionic form, amino acid, 3-Aminobutanoic acid, IR and Raman spectra, DFT calculations, hydrogen bonded dimer.

Total Refs : 14

A study of vibrational spectra of zwitterionic 3-Aminobutanoic acid, as supported by density functional calculations.pdf

---

 Vol. 24, No 5 (2015) 713-720

Spectroscopic and quantum chemical characterization of 2-Phenoxyacetohydrazide

 

Semiha Bahçeli^1* and Halil Gökce²

¹Department of Physics, Faculty of Arts and Science, Süleyman Demirel University,
East Campus, 32260, Isparta, Turkey
²Vocational High School of Health Services, Giresun University, Güre Campus, 28200, Giresun, Turkey
Dedicated to Prof J R Durig

---

In the present study, the quantum chemical calculations of 2-phenoxyacetohydrazide, (C8H10N2O2), as a biologically active compound have been verified by using the density functional theory (DFT) method. The optimized molecular geometry, vibrational wavenumbers, electronic absorption spectrum (in vacuum and ethanol solvent) and 1H and 13C NMR chemical shifts (in chlorofom solvent), the HOMO-LUMO and natural bond (NBO) analyses, the molecular electrostatic potential (MEP), thermodynamic properties and atomic charges of title molecule have been computed by using the DFT/B3LYP calculation method with 6-311++G(d,p) in the ground state. The calculated fundamental vibrational frequencies are found to be good agreement with observed results. © Anita Publications. All rights reserved.
Keywords: 2-Phenoxyacetohydrazide; Vibrational Spectroscopy; Electronic Absorption Spectroscopy;  Density Functioal Theory.

Total Refs :46

---

 Vol. 24, No 5 (2015) 721-727

DFT based vibrational spectral characterisation of mineral: Diopside

 

J Binoy^a and V S Jayakumar^b*

^aDepartment of Physics, Government College, Nedumangad, Thiruvananthapuram-695 541, India

^bMar Baselios Institute of Technology, Anchal, Kollam District, Kerala, India

Dedicated to Prof J R Durig

---

ne and glass ceramics manufacturing. The present investigation deals with the geometry optimization of the formula units of minerals followed by the computation of vibrational spectra using density functional theoretical (DFT) method at B3LYP/LANL2DZ level. The vibrational spectral analysis has been undertaken using Fourier transform infrared and Fourier transform Raman spectra with the aid of DFT computed spectra. The intermolecular interactions among formula units, responsible for network formation, have been explored using vibrational spectra, supported by electrostatic potential (ESP) mapping studies. © Anita Publications. All rights reserved.

Total Refs : 9

---

 Vol. 24, No 5 (2015) 729-736

NLO activity in 1-(Diamino methylene)
Thiouron-1-ium perchlorate: A theoretical analysis

 

V R Suresh Kumar^a, J Binoy^b, S Dawn Dharma Roy^a, M K Marchewka^c and V S Jayakumar^a*

^aDepartment of Physics, N M Christian College, Marthandam, Tamil Nadu, INDIA

^bDepartment of Physics, Government College, Nedumangadu, Thiruvananthapuram, Kerala, INDIA

^cInstitute of Low Temperature and Structure Research, Polish Academy of Sciences, Okolna 2, 50-422 Wroclaw, Poland

Dedicated to Prof J R Durig

---

The reduction of NLO activity of 1-(Diamino methylene) thiouron-1-ium (DMT), an interesting compound for nonlinear activity, upon addition of perchlorate to form 1-(Diamino methylene) thiouron-1-ium perchlorate (DMTC) has been subjected under theoretical investigation using density functional theory at B3LYP/6-311 G (d, p) level. The geometry correlates well with XRD pattern. The calculations show that DMT has NLO efficiency of 55 and DMTC has 22 times that of urea. The HOMO – LUMO analysis points to the existence of conjugated path responsible for intramolecular charge transfer, which contributes to NLO activity. The molecular electrostatic potential (MEP) mapping has been performed for the analysis of the mutual interaction of DMT and (DMTC), which leads to reduction in NLO activity of DMTC. Natural Bond Orbital (NBO) analysis provides insight to the bypass of charge transfer through hydrogen bonding, upon addition of perchlorate to DMT, responsible for the reduction of NLO activity. © Anita Publications. All rights reserved.

Total Refs : 14

---

 Vol. 24, No 5 (2015) 777-782

DFT study on the Rh₃Zr and Rh₃Nb compounds

 

G Surucu ^1*, K Colakoglu², N  Korozlu ^3,4 and C Kaderoglu^5
1Department of Electric and Energy, Ahi Evran University, 40100 Kırşehir, Turkey
²Department of Physics, Gazi University, 06500 Ankara, Turkey
³Department of Physics, Erzincan University, Yalnizbag, 24100 Erzincan, Turkey
⁴Nuclear Sciences Application and Research Center, Akdeniz University, 07058 Antalya, Turkey
⁵Department of Engineering Physics, Ankara University, Ankara, Turkey

---

Due to the attractive high-temperature physical properties, platinum metal-base alloys such as Rh-base alloys make them important materials for various technological applications. To understand deeply the structural, and lattice dynamical properties of the L12-type (space number 221) of intermetallic compounds Rh₃Zr and Rh₃Nb, we have performed ab-initio density-functional theory within the local density approximation (LDA). Specifically, the phonon dispersion curves and corresponding one-phonon density of states (DOS) for both compounds are computed. Some basic physical parameters such as lattice constant, bulk modulus, elastic constants, shear modulus, Young’s modulus, and Poison’s ratio are also calculated. Our structural results are consistent with the available experimental and other theoretical data. © Anita Publications. All rights reserved.
Keywords: Lattice Dynamic; Elastic properties; Thermal properties; Ab-initio calculations.

Total Refs : 36

DFT study on the Rh3Zr and Rh3Nb compounds.pdf

---

 Vol. 24, No 5 (2015) 00-00

Density functional theory calculation and vibrational spectroscopic study of p-Hydroxy benzoic acid dimer

 

V Bena Jothy^a,b , M Amalanathan^a , V K Rastogi^c,d and I Hubert Joe^a*
^aCentre for Molecular and Biophysics Research, Department of Physics, Mar Ivanios College,
Thiruvananthapuram-629 015, India
^bDepartment of Physics, Women’s Christian College, Nagercoil – 629 001, Tamil Nadu, India
^cIndian spectroscopy society, K.C 68/1, Old Kavi Nagar, Ghaziabad-201 002, U.P, India
^dDepartment of Physics, CCS University, Meerut-250 004,  India

---

p-Hydroxybenzoic acid is subjected to vibrational spectral investigation using NIR-FT-Raman, and FTIR. The geometry and vibrational spectra of p-hydroxybenzoic acid dimer have been computed using B3LYP level 6-31G(d) basis set. Vibrational spectral investigation confirms the formation of strong O-H…O hydrogen bonding between the carbonyl oxygen lone electron pairs and the O-H σ* antibonding orbitals. The red-shift of the O-H stretching wavenumbers suggests the existence of strong intermolecular O-H…O hydrogen bonding, which is justified by the natural bond orbital (NBO) analysis. © Anita Publications. All rights reserved.