Self-consistent Reaction Field Theory Research Articles

C-PCM study on the electronic and optical properties of Fe(CO)4B12N12 complexes

We explored solvent effect on the stability, dipole moment, polarizability and first hyperpolarizability of Fe(CO)4B12N12 complexes at MPW1PW91/6-311G(d,p) level of theory. These complexes were considered in the low spin states. The self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (PCM) was employed to illustration of the solvent influences. The relations between the parameters with solvent polarity functions (McRae and Suppan functions) were given. Also, relations of the wavenumbers values of the stretching of carbonyl ligands with the Kirkwood–Bauer–Magat equation (KBM) were provided.

Exploration of the Electronic, Spectroscopic Properties, and Bonding of an Antimalarial Drug of Chromium Arene–Quinoline Half Sandwich Complex in Aqueous Solution: A PCM Investigation

In this paper, using the mPW1PW91 functional, quantum chemical calculations were used to explore electronic, spectroscopic properties and bonding of an antimalarial drug of chromium arene–quinoline half sandwich complex in gas and aqueous phases. The solvent effects were examined using the self-consistent reaction field theory (SCRF) based on the polarizable continuum model (PCM). Reactivity parameters of the complex and chloroquine were compared. The molecular properties of these molecules were related to their biological activity. The studied complex and chloroquine's octanol-water partition coefficient (log P) were calculated and compared. The correlation between molecular hardness and biological activity was illustrated. The temperature dependence of thermodynamic parameters of the complex was investigated. Cr-C bonds in the studied drug were illustrated using NBO and QTAIM analyses.

Computational investigation of the solvent and temperature effects on the tautomerization of 7-amino-1,3-dioxo-2,5-diphenyl-2,3-dihydro-1H, 5H-pyrazolo[1,2-a][1,2,4]triazole-6-carbonitrile

This research examines the effects of solvent polarity and temperature on the tautomerization of 7-amino-1,3-dioxo-2, 5-diphenyl-2,3-dihydro-1H,5H-pyrazolo[1,2-a][1,2,4]triazole-6-carbonitrile at CAM-B3LYP/6-311G (d,p) level of theory. The selected solvents are n-hexane, diethyl ether, pyridine, ethanol, methanol, and water. The solvent effects have been examined by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects have been explored on the energy barrier, frontier orbitals energies, and HOMO-LUMO gap. Dependencies of thermodynamic parameters (DG andDH) on the dielectric constants of solvents have also been tested. Specifically, the temperature dependencies of the thermodynamics parameters have been studied within 100-1000 K range. The rate constant of the tautomerism reaction is computed from 300 to 1200 K, in the gas phase.

Complex formation of titanocene dichloride anticancer and Al12N12 nano-cluster: A quantum chemical investigation of solvent, temperature and pressure effects

This study investigated the interaction between Al12N12 nano-cluster and titanocene dichloride anticancer drug complex using B3P86 functional in gas and solution phases. Non-covalent interaction (NCI) analysis of this complex was employed for illustration of the Cl⋯Al weak non-covalent interaction. The self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM) was applied for testing the solvent effects. The solvent effect on the interaction energy, dipole moment, frontier orbital energy, and global reactivity parameters was examined as well. The changes in the dipole moment, polarizability and electronic spatial extent (ESE) with solvent polarity were analyzed by applying different solvent polarity parameters based on Lippert-Mataga, Bakhshiev and Bilot-Kawski models. In addition, temperature and pressure effects on the thermodynamic parameters of this interaction were illustrated.

Solvent and temperature effects on the tautomerization of a carbonitrile molecule: A conductor-like polarizable continuum model (CPCM) study

This research examined the effects of solvent polarity and temperature on the tautomerization of a carbonitrile molecule at CAM-B3LYP/6-311G (d,p) level of theory. The selected solvents were n-hexane, diethyl ether, pyridine, ethanol, methanol, and water. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and HOMO-LUMO gap. Dependencies of thermodynamic parameters (ΔG and ΔH) on the dielectric constants of solvents were also tested. Specifically, the temperature dependencies of the thermodynamics parameters were studied within 100–1000 K range. The rate constant of the tautomerism reaction was computed from 300 to 1200 K, in the gas phase.

Unveiling the influence of solvent polarity on structural, electronic properties, and 31P NMR parameters of rhenabenzyne complex

In this paper, using the mPW1PW91 functional, quantum chemical calculations were employed to explore the effect of solvent on structure, electronic, reactivity, and 31P NMR chemical shift values of a rhenabenzyne complex. The solvent effects were examined using the self-consistent reaction field theory (SCRF) based on the conductor-like polarizable continuum model (CPCM). Aprotic and protic solvents were also selected. The correlations of the dipole moment and polarizability values with solvent polarity functions including both the dielectric constant (ε) and refractive index (nD) of the liquid medium were illustrated further. Fukui function and dual descriptor were used to reveal the study favorable site of electrophilic attack.

Structure, electronic properties and slippage of cyclopentadienyl and indenyl ligands in the (η5-C5H5) (η3-C5H5) W(CO)2 and (η5-C9H7) (η3-C9H7)W(CO)2 complexes: A C-PCM investigation

The structure, electronic properties, and the slippage of cyclopentadienyl and indenyl ligands in the (η5-C5H5) (η3-C5H5)W(CO)2 and (η5-C9H7)(η3-C9H7)W(CO)2 were illustrated by applying the mPW1PW91 functional. The solvent impacts were surveyed by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM).The behavior of these compounds was investigated by studying the dipole moment and carbonyl stretching frequencies in solvents of different polarities such as tetrahydrofuran (THF), dichloromethane (DCM), cyclohexanone (CH), ortho-nitrotoluene (NT), Propanonitrile (PN), Acetonitrile (AN), Dimethylsulfoxide (DMSO). The correlations of dipole moment values with Lippert–Mataga polarity function, Bakhshiev polarity function and Bilot and Kawski were illustrated. Also, correlations of the calculated carbonyl stretching frequencies (ν(CO)) with the Kirkwood–Bauer–Magat equation (KBM) were explored. Natural bond orbital analysis (NBO) was utilized for illustration of the W–C bonds in the studied complexes.

Cyclometalation in the (η3-C5H5)Co(η2-C2H2)(PMe3) and (η3-C9H7)Co(η2-C2H2) (PMe3) complexes: A computational investigation

This research examined the cyclometalation in the (η3-C5H5)Co(η2-C2H2)(PMe3) and (η3-C9H7)Co(η2-C2H2)(PMe3) complexes by using mPW1PW91 functional. Thermodynamic and kinetic parameters of this reaction were computed. The solvent effects were studied by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and reactivity parameters (hardness, chemical potential, electrophilicity). The Hirshfeld population analysis was performed based on optimized structures. The rate constant of the cyclometalation reaction was computed from 300 to 1200 K, in the gas phase. In addition, the synchronicity values of this reaction were determined. Our findings revealed, this reaction was favorable energetically in both gas and solution phases. The larger rate constant values were in the presence of Cp ring than In ring.

Theoretical study of the influence of solvent polarity on the 31P and 13C NMR parameters of the Ru(PH3)4(η2-benzyne) complex

In this study, using the wB97XD method, quantum chemical calculations were used to analyze the effect of solvent on 31P and 13C NMR parameters of the Ru(PH3)4(η2-benzyne) complex. The solvent effects were examined using the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM). The stability of this complex was studied in the singlet and triplet states. The 31P and 13C NMR chemical shifts of the complex were calculated for both gas and solution phases. One-bond nuclear spin–spin coupling constants of RhC and RuP bonds as well as two-bond nuclear spin–spin coupling constants of P⋯P were estimated. The correlations of these parameters and solvent polarity functions including both the dielectric constant (ε) and refractive index (nD) of the liquid medium were explored further. In addition, the most significant Ramsey terms involved significantly in 1J(RuP), 1J(RuC) and 2J(P⋯P) values were determined. Finally, the correlations between 1J(RuP), 1J(RuC) and the APT net charge on the Ru atom were studied.

Research on micro mechanism of water-based disperse ink and optimization of driving waveform for inkjet ink

In this paper, we use density functional theory (DFT) to optimize and calculate the geometries and vibration frequencies of H2O, EG (ethylene glycol) or H2O/EG in the ink (B3LYP/6-311++G** basis set, self-consistent reaction field theory (SCRF) and PCM polarization unified field model). LF-NMR (low-filed nuclear magnetic resonance) further confirmed the weak interaction between H2O, EG or H2O/EG molecules, which had a decisive influence on the viscosity and mobility of ink. According to the analysis of the peak of the inversion spectrum (T22) of the ink, the viscosity of the ink increases with the left shift of the relaxation time. The inkjet performance of the ink is closely related to the physicochemical properties of the ink and the driving waveform of the piezoelectric nozzle. Exploration of the sharpness of the inkjet printing pattern that the microstructure and weak intermolecular interaction of the ink bounds the mobility of the solvent in the ink, which increases the viscosity of the ink (3.28-5.11 mPa.s), and the ink overcomes the capillary effect of the fabric, which makes the diffusion of the ink in the fabric decrease (7.23-3.91 %).

Theoretical understanding the effects of external electric field on the hydrolysis of anticancer drug titanocene dichloride

In this study, hydrolysis of the anticancer drug titanocene dichloride complex in the absence and presence of external electric field (EEF) was studied using quantum mechanical methods in the gas phase and aqueous solution. BP86 functional and basis sets of 6-311G(d,p) and Def2-TZVPPD for main group element and Ti atoms, respectively, were employed in these calculations. The effects of solvent were studied by means of the self-consistent reaction field theory on the basis of the Polarizable Continuum Model. Two typical reactions involved in the complex hydrolysis include the first and second hydrolysis processes. It was tired to show how the total energy, barrier energy, thermodynamic and kinetic parameters of titanocene dichloride hydrolysis were affected by the EEF. In addition, variations of the structural parameters were illustrated in the absence and presence of EEF. The structural-properties correlations between these parameters and the strength of EEF were provided.

Effect of the Solvent Polarity on the Optical Properties in the (OC)5Cr=(OEt)(Ph) Complex: A Quantum Chemical Study

In this study, using the B3LYP* method, quantum chemical computations were applied for analyzing the effects of solvent on the electronic spectrum features of the (OC)5Cr=(OEt)(Ph) complex. The effects of solvent were studied by means of the self-consistent reaction field theory (SCRF) on the basis of the Polarizable Continuum Model (PCM). The relations between the dipole moment values and solvent polarity functions including both the dielectric constant (e) and refractive index (nD) corresponding to the aqueous media, were studied. The most intensity electronic transition of the complex (λmax) was determined in gas and solution phases. The relations between λmax values and the Kirkwood–Bauer–Magat equation (KBM) derived from this equation were studied. The natural transition orbitals (NTOs) was utilized for illustration of the nature of the most intensity electronic transition in the examined complex. Also, Linear solvation energy relationship of Kamlet–Taft was rationalized solvent have influence on the λmax values. Hyperpolarizability values of this complex were calculated in gas and solution phases and their correlations with solvent polarity functions were illustrated.

Theoretical Analysis of Solvent Polarity Effect on the Electronic and Spectroscopic Properties (IR and UV) of the Ni(CO)2(NHC)2 Complex (NHC = 1H-Imidazol-2-ylidene)

In this study, using the wB97XD functional, quantum chemical calculations were used to analyze the solvent effect on the structural, electronic and spectroscopic (IR and UV) features of the Ni(CO)2(NHC)2 complex (NHC = 1H-imidazol-2-ylidene). Using the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM), the solvent effects were examined. The solvation model utilized the radii and non-electrostatic terms of the solvent model density (SMD). The linear correlations between these parameters and solvent polarity functions including both the dielectric constant (e) and refractive index (nD) of the liquid medium, were explored. Correlations of the calculated spectral parameters ($${v}$$(CO) and λmax) with the Kirkwood–Bauer–Magat equation (KBM) and improved form of this equation were explored. The natural transition orbitals (NTOs) was utilized for illustration of the nature of the most intense electronic transition in the studied complex.

The Impact of Solvent Polarity on the Stability, Electronic Properties, and 1H NMR Chemical Shift of the Conformers of 2-Chloro-3-Methylcyclohexan-1-One Oxime: a Conceptual DFT Approach

In this article, the stability of the conformers of 2-chloro-3-methylcyclohexan-1-one oxime was investigated at the wB97XD/6-311G(d,p) level of theory. Using the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM), the solvent impacts were examined. Solvent influence on the total energy, relative energy, dipole moment, the energies of frontier orbitals, and proton chemical shift of these molecules were investigated. The associations between these parameters and solvent polarity functions including both the dielectric constant (e) and refractive index (nD) of the liquid medium were found. Moreover, NBO analysis was used to illustrate the hyperconjugative anomeric effect on the conformers.

Computational investigation of solvent polarity effect on the structure and properties of a (OC)4Cr-biscarbene complex in the singlet ground state and lowest singlet excited state

In this study, using the MPW1PW91 functional, quantum chemical calculations were used to analyze the solvent effect on the energy, dipole moment, structural parameters, frontier orbital energy, and wavelength of the strongest absorption band (λmax,el) of a (OC)4Cr-biscarbene complex at the singlet ground state (S0) and lowest singlet excited state (S1). Using the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM), the solvent effects were examined. Employing Lippert-Mataga, Bakhshiev and Kawski models, we found that linear correlations provided a satisfactory description of polarity effect of solvents on this complex. Additionally, correlations of the calculated λmax values with the Kirkwood–Bauer–Magat equation (KBM) and improved form of this equation were explored. The natural transition orbitals (NTOs) was utilized for illustration of the nature of the wavelength of the strongest absorption band in the studied complex.

Theoretical Analysis of Solvent Effect on the NMR Parameters in trans-(NHC)PtI2Py Complex: A Platinum-Based Anticancer Drug

In this study, quantum chemical calculations using MPW1PW91 method were applied to analyze the solvent effect on the NMR parameters for a platinum-based anticancer drug, namely complex trans-(NHC)PtI2Py. The solvent effects on isotropic magnetic shielding tensor data (σiso) for Pt and CNHC atoms and spin–spin coupling constants of Pt–C and Pt–N in the complex were studied by the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM). The linear correlations between these parameters and dielectric constants of solvents were studied. The σiso (Pt) values in different solvents were correlated with the Kirkwood–Bauer–Magat equation (KBM).

Unveiling Noncovalent Interactions in Imidazolium, Pyrrolidinium, or Quaternary Ammonium Cation and Acetate Anion Based Protic Ionic Liquids: Structure and Spectral Characteristics.

In the present work protic ionic liquids (PILs) composed of imidazolium-, quaternary ammonium-, or pyrrolidinium-dications and acetate (OAc-) anion have been modeled as the dication-anion complexes through the M06-2x based density functional theory. It has been shown that cation-anion interaction energies are larger for the PILs containing the quaternary ammonium cation, which can be attributed to strong hydrogen bonding from the terminal ammonium protons. Underlying N-H···O and C-H···O hydrogen bonding, electrostatic, and van der Waals interactions are unraveled using the natural bond orbital analyses in conjunction with the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction index reduced density gradient methods. The ramifications of noncovalent binding to 1H NMR and vibrational spectra are presented. The calculations further demonstrate a linear correlation of the kinetic energy density parameter G( r) in QTAIM analysis with the characteristic frequency shift of -NH3+ stretching in the dication-anion complexes. Moreover, the chemical shifts (δH) in 1H NMR spectra from theory reveal larger deshielding; the corresponding δH value correlates well with proton affinities and cation-anion binding energies as well. Effect of solvent (DMSO) on structure, binding energies, and 1H NMR are presented. The shifts of the characteristic carbonyl and the terminal ammonium stretching vibrations accompanying the dication-anion complexes from gas phase calculations are in consonance with the self-consistent reaction field theory.

Influence of Solvent and Electric Field on the Structure and IR, 31P NMR Spectroscopic Properties of a Titanocene–Benzyne Complex

The effect of solvent on the structural, frontier orbital energies, global density-based descriptors, vibrational frequencies, and 31P NMR chemical shifts was examined for the syn-Cp2Ti(η2-C6H4-2-OMe)(PMe3) complex by the self-consistent reaction field theory (SCRF) based on the polarizable continuum model (PCM). The studied spectroscopic parameters were correlated with the Kirkwood–Bauer–Magat (KBM) equation. Also, the response of the global density-based descriptors (chemical potential and hardness) in the presence of external electric field was studied. EDA, QTAIM, ELF, LOL, and NBO analyses were used for illustration of the Ti–C bond in this complex.

The Influence of Solvent on the Structural Properties of trans-(NHC)PtI2Py Complex: A Platinum-Based Anticancer Drug

Quantum chemical calculations using MPW1PW91 method were applied to analyze the solvent effect on the structural, spectral, and thermochemical parameters for a platinum-based anticancer drug trans-(NHC)PtI2Py complex. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on Polarizable Continuum Model (PCM). The linear correlations between the solvation energies, HOMO–LUMO gaps, IR-active stretching vibration of Pt–N bonds and N–H of NHC ligand with dielectric constants of solvents were studied. The wave numbers of these IR-active stretching vibrations in different solvents were correlated with the Kirkwood–Bauer–Magat equation (KBM). The thermodynamic activation parameter such free energy of solvation, enthalpy of solvation were also calculated.

A quantum chemical investigation of the influence of solvent polarity on the structural, electronic, spectroscopic properties and hyperpolarizability in Molybdenum Silylidyne complex CpMo(CO)2([tbnd]Si[sbnd]Ph)

In this study, quantum chemical calculations using MPW1PW91 method was applied to analyze of solvent effect on the structural, 13C and 29Si NMR chemical shifts, vibrational analysis, thermochemical parameters and first hyperpolarizability for CpMo(CO)2(SiPh) complex. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on Polarizable Continuum Model (PCM). The correlations between these parameters and solvent polarity functions, involve both the dielectric constant (ε) and refractive index (nD) of the liquid medium were explored. Correlations of the calculated spectral parameters (υ(CO), δ(13C) and δ(29Si)) with the Kirkwood–Bauer–Magat equation (KBM) and improved form of this equation were explored.