scholarly journals Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

2016 ◽  
Vol 2016 ◽  
pp. 1-19 ◽  
Author(s):  
Nyiang Kennet Nkungli ◽  
Julius Numbonui Ghogomu
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Broad Band ◽  
Solvent Polarity ◽  
Dielectric Constants ◽  
Dft Study ◽  
Electromagnetic Spectrum ◽  
Metal Chelation ◽  
First Hyperpolarizability ◽  
Nlo Response

Nonlinear optical (NLO) properties of organic and metal-organic materials are of considerable interest to emerging optoelectronic and photonic technologies. Much work has been carried out on the former materials but the latter ones have received less attention till date. Herein, a density functional theory (DFT) study on the combined effects of transition metal chelation and solvent polarity on the first hyperpolarizability (βtot) of 4-methoxyacetophenone thiosemicarbazone (MAPTSC) is reported. MAPTSC exhibits a tautomeric form with higher optical nonlinearity rendering its NLO response in polar solvents potentially switchable. Our results have revealed significant modifications of the first hyperpolarizability of MAPTSC upon complexation with different transition metal chlorides in the presence of solvents with varying dielectric constants. Therefore, its second-order NLO response is highly tunable by the synergy of transition metal chelation and solvent polarity. MAPTSC and its Zn(II) and Pt(II) chloride complexes are promising NLO materials because their gas-phase βtot values are larger than those of the prototype push-pull molecules, para-nitroaniline (PNA) and urea, by factors of about 1.40–1.76 and 19.57–37.24, respectively; these factors greatly increase in polar solvent medium. Moreover, they possess high optical transparencies in the visible region of the electromagnetic spectrum which mitigate transparency/nonlinearity trade-offs, thereby increasing the likelihood of broad band NLO response.

scholarly journals Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

2019 ◽  
Author(s):  
Pralok K. Samanta ◽  
Md Mehboob Alam ◽  
Ramprasad Misra ◽  
Swapan K. Pati
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Photon Absorption ◽  
First Hyperpolarizability ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Nlo Response ◽  
Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

scholarly journals Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

2019 ◽  
Author(s):  
Pralok K. Samanta ◽  
Md Mehboob Alam ◽  
Ramprasad Misra ◽  
Swapan K. Pati
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Photon Absorption ◽  
First Hyperpolarizability ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Nlo Response ◽  
Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

scholarly journals Effect of Stone–Wales defects and transition-metal dopants on arsenene: a DFT study

RSC Advances ◽  
2019 ◽  
Vol 9 (33) ◽  
pp. 19048-19056 ◽  
Author(s):  
Jialin Li ◽  
Qingxiao Zhou ◽  
Weiwei Ju ◽  
Qian Zhang ◽  
Yanling Liu
Keyword(s):  
Density Functional Theory ◽  
Magnetic Properties ◽  
Transition Metal ◽  
Density Functional ◽  
Dft Study ◽  
Functional Theory ◽  
Electronic And Magnetic Properties

The structural, electronic, and magnetic properties of 3d transition metal (TM) atom (Sc, V, Cr, Mn, Co, and Cu) doped Stone–Wales (SW) defect arsenene were systematically investigated by density functional theory (DFT).

Electronic properties of double-atom catalysts for electrocatalytic oxygen evolution reaction in alkaline: A DFT study

Nanoscale ◽  
2021 ◽  
Author(s):  
Chunhua Yang ◽  
Yang Wu ◽  
Yuxiu Wang ◽  
He-Na Zhang ◽  
Liang-Hui Zhu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Transition Metal ◽  
Electronic Properties ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Density Functional ◽  
Dft Study ◽  
Functional Theory ◽  
Metal Atoms ◽  
Transition Metal Atoms

In alkaline, the electrocatalytic oxygen evolution reaction (OER) of dual transition metal atoms (2TM) nitrogen-decorated graphene as double-atom catalysts (DACs) has received special attention. Here, using density functional theory (DFT)...

Tuning the structural, electronic and dynamical properties of Janus M4X3Y3 (M = Pd, Ni and Co; X,Y = S, Se and Te) monolayers: a DFT study

2021 ◽  
Vol 23 (37) ◽  
pp. 21139-21147
Author(s):  
Ismail Eren ◽  
Berna Akgenc
Keyword(s):  
Density Functional Theory ◽  
Transition Metal ◽  
Density Functional ◽  
Dft Study ◽  
Vibrational Properties ◽  
Metal Chalcogenides ◽  
Two Dimensional ◽  
Functional Theory ◽  
Transition Metal Chalcogenides ◽  
Dynamical Properties

Based on density functional theory, the structural, electronic and vibrational properties of two-dimensional transition metal chalcogenides M2X3 and their Janus type M4X3Y3, where M = Pd, Co and Ni and X = Se, S and Te, are investigated.

scholarly journals A DFT Study of Structural and Bonding Properties of Complexes Obtained from First-Row Transition Metal Chelation by 3-Alkyl-4-phenylacetylamino-4,5-dihydro-1H-1,2,4-triazol-5-one and Its Derivatives

2017 ◽  
Vol 2017 ◽  
pp. 1-15 ◽  
Author(s):  
Hubert Jean Nono ◽  
Désiré Bikélé Mama ◽  
Julius Numbonui Ghogomu ◽  
Elie Younang
Keyword(s):  
Transition Metal ◽  
Gas Phase ◽  
Metal Atom ◽  
Density Functional ◽  
Antioxidant Activities ◽  
Metal Chelation ◽  
Topological Parameters ◽  
Bonding Properties ◽  
Neutral Ligands ◽  
Phase Water

Density functional calculations were used to explore the complexation of 3-alkyl-4-phenylacetylamino-4,5-dihydro-1h-1,2,4-triazol-5-one (ADPHT) derivatives by first-row transition metal cations. Neutral ADPHT ligand and mono deprotonated ligands have been used. Geometry optimizations have been performed in gas-phase and solution-phase (water, benzene, and N,N-dimethylformamide (DMF)) with B3LYP/Mixed I (LanL2DZ for metal atom and 6-31+G(d,p) for C, N, O, and H atoms) and with B3LYP/Mixed II (6-31G(d) for metal atom and 6-31+G(d,p) for C, N, O, and H atoms) especially in the gas-phase. Single points have also been carried out at CCSD(T) level. The B3LYP/Mixed I method was used to calculate thermodynamic energies (energies, enthalpies, and Gibb energies) of the formation of the complexes analyzed. The B3LYP/Mixed I complexation energies in the gas phase are therefore compared to those obtained using B3LYP/Mixed II and CCSD(T) calculations. Our results pointed out that the deprotonation of the ligand increases the binding affinity independently of the metal cation used. The topological parameters yielded from Quantum Theory of Atom in Molecules (QTAIM) indicate that metal-ligand bonds are partly covalent. The significant reduction of the proton affinity (PA) observed when passing from ligands to complexes in gas-phase confirms the notable enhancement of antioxidant activities of neutral ligands.

DFT study on endohedral and exohedral B38fullerenes: M@B38(M = Sc, Y, Ti) and M&B38(M = Nb, Fe, Co, Ni)

2015 ◽  
Vol 17 (32) ◽  
pp. 20897-20902 ◽  
Author(s):  
Qi Liang Lu ◽  
Qi Quan Luo ◽  
Yi De Li ◽  
Shou Guo Huang
Keyword(s):  
Density Functional Theory ◽  
Transition Metal ◽  
Density Functional ◽  
Dft Study ◽  
Functional Theory ◽  
Metal Atoms ◽  
Transition Metal Atoms

Viability of endohedral and exohedral B38fullerenes with transition metal atoms was investigated using density functional theory. M@B38(M = Sc, Y, Ti) possess endohedral structures as their lowest energy structures.

Density Functional Calculations of EPR Parameter g Tensors of Some Transition Metal Complexes

2011 ◽  
Vol 2 (2) ◽  
pp. 139-141
Author(s):  
Vinita Prajapati ◽  
◽  
P.L.Verma P.L.Verma ◽  
Dhirendra Prajapati ◽  
B.K.Gupta B.K.Gupta
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional Calculations ◽  
Density Functional
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