• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.355-363
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• 2023

In this study, we explore the nature of clumped isotopes of H₂O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (¹⁶O, ¹⁷O, and ¹⁸O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H₂O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT¹⁸O), 1.16 times (HT¹⁷O), and 0.703 times (HD¹⁷O) relative to HD¹⁸O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H₂O including ¹⁷O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H₂O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

• Journal of the Korean Chemical Society
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• v.56 no.2
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• pp.195-200
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• 2012

In this study we present a new approach for computing the partial atomic charge derived from the wavefunctions of molecules. This charge, which we call the "y_charge", was calculated by taking into account the energy level and orbital populations in each molecular orbital (MO). The charge calculations were performed in the software, which was developed by us, developed using the C# programming language. Partial atomic charges cannot be calculated directly from quantum mechanics. According to a partitioning function, the electron density of constituent molecular atoms depends on the electrostatic attraction field of the nucleus. Taking into account the Boltzmann population of each MO as a function of its energy and temperature we obtain a formula of partial charges.

• Journal of Korean Vacuum Science & Technology
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• v.6 no.1
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• pp.43-45
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• 2002

We have theoretically investigated steady-state carrier transport and current self-oscillation in negative-effective-mass (NEM) p$\^$+/pp$\^$+/diodes. The current self-oscillation here is a result of the formation and traveling of electric field domains in the p base having a NEM. The dependence of self-oscillating frequency on the applied dc voltage is obtained by detailed numerical simulations. In the calculations, we have considered the scatterings by carrier-impurity, carrier-acoustic phonon, carrier-polar-phonon, and carrier-nonpolar-phonon-hole interactions . This kind of NEM oscillator allows us to reach a current oscillation with terahertz frequency, thus it may be used as a broadband source of terahertz radiation.

• ETRI Journal
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• v.22 no.3
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• pp.19-26
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• 2000

We describe a detailed numerical scheme to calculate electron transport in quantum wires using the Green function formalism combined with tight-binding orbital basis. As an example of the application, we study the electron transport in a Si nanowire containing a finite potential barrier. The effects of nonzero bias, temperature, and disorder on the barrier-induced oscillatory conductance are investigated within the context of coherent transport model. The oscillatory behavior of the conductance as a function of the Fermi energy is found to be highly sensitive to sample disorder and limited to a very low temperature and a small bias range.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• Journal of the Korean Chemical Society
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• v.57 no.4
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• pp.461-471
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• 2013

Optimized geometrical structure, atomic charges, molecular electrostatic potential, nonlinear optical (NLO) effects and thermodynamic properties of the title compound N-(2,5-methylphenyl)salicylaldimine (I) have been investigated by using ab initio quantum chemical computational studies. Calculated results showed that the enol form of (I) is more stable than keto form. The solvent effect was investigated for obtained molecular energies, hardneses and the atomic charge distributions of (I). Natural bond orbital and frontier molecular orbital analysis of the title compound were also performed. The total molecular dipole moment (${\mu}$), linear polarizability (${\alpha}$), and first-order hyperpolarizability (${\beta}$) were calculated by B3LYP method with 6-31G(d), 6-31+G(d,p), 6-31++G(d,p), 6-311+G(d) and 6-311++G(d,p) basis sets to investigate the NLO properties of the compound (I). The standard thermodynamic functions were obtained for the title compound with the temperature ranging from 200 to 450 K.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.243-243
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• 2012

Self-assembled monolayers (SAMs) prepared by aromatic thiols on gold surfaces have much larger potential for electronic device applications due to their electronic properties. In this study, the formation and structures of SAMs prepared by benzenethiol (BT), toluenethiol (TT), 2-fluorobenzenethiol (2-FBT), 3-fluorobenzenethiol (3-FBT), 4-fluorobenzenethiol (4-FBT), 4-chlorobenzenethiol (4-CBT), 4-fluorobenzenemethanethiol (4-FBMT), and 4-chlorobenzenemethanethiol (4-CBMT) on Au(111) were examined using scanning tunneling microscopy (STM) and Kelvin probe (KP) to explore the structure and electronic interface properties of eight differently substituted aromatic thiol SAMs on Au(111). And these values are compared with gas phase dipole moments computed by quantum chemical calculations for individual thiol molecules. It was revealed that all eight thiol-molecules form uniform SAMs on Au(111) at $75^{\circ}C$ compared to lower solution temperature by STM observation. The work function change obtained in the KP measurements and calculated molecular dipole moments have the linear relationship while the 4-FBMT and 4-CBMT deviate from this tendency.

• Proceeding of EDISON Challenge
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• 2017.03a
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• pp.128-131
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• 2017

We explore the inverse electron demand Diels-Alder reactions of tetrazines with various functional groups employing quantum calculations. In general, the rate of inverse electron demand Diels-Alder reaction depends on molecular orbital levels of electron donor and electron acceptor. Likewise, ${\pi}$ orbital of the dienophile and ${\pi}^*$ orbital of the diene is a key factor. In this work, we discuss the case where the energy of diene's ${\pi}^*$ molecular orbital is not the sole governing factor to determine the reaction rate, rather the rate shows strong correlation with the charge density of dienes.

• Journal of Electrochemical Science and Technology
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• v.6 no.1
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• pp.7-15
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• 2015

3-(4-Iodophenyl)-2-imino-2,3-dihydrobenzo[d]oxazol-5-yl 4-methylbenzenesulfonate (4-IPhOXTs) was synthesized and its inhibiting action on the corrosion of stainless steel 316L (SS) in sulfuric acid was investigated by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results of the investigation show that this compound has excellent inhibiting properties for SS corrosion in sulfuric acid. Inhibition efficiency increases with increase in the concentration of the inhibitor. The adsorption of 4-IPhOXTs onto the SS surface followed the Langmuir adsorption model with the free energy of adsorption ΔG⁰_ads of −8.45 kJ mol⁻¹ . Quantum chemical calculations were employed to give further insight into the mechanism of inhibition action of 4-IPhOXTs.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.891-896
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• 2002

The structures and energies of p-tert-butylcalix[4]crown-6-ether(1) in various conformers and their alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. We have tried to obtain the relative affinity of partial-cone and 1,3-alternate conformers of 1 for alkyl ammonium guests by comparison with its cone-shaped analogue. We have also calculated the relative complexation efficiency of these host-guest complexes focusing on the binding sites of $crown-\sigma-enther$ moiety or benzene-rings pocket of the host molecule 1. These calculations revealed that the crown moiey has better complexation efficiency than upper rim part of calyx[4]arene that is in similar trend to the cone-shaped complexes.