• 제목/요약/키워드: Density functional calculation

검색결과 122건 처리시간 0.027초

TDDFT Potential Energy Functions for Excited State Intramolecular Proton Transfer of Salicylic Acid, 3-Aminosalicylic Acid, 5-Aminosalicylic Acid, and 5-Methoxysalicylic Acid

  • Jang, Sung-Woo;Jin, Sung-Il;Park, Chan-Ryang
    • Bulletin of the Korean Chemical Society
    • /
    • 제28권12호
    • /
    • pp.2343-2353
    • /
    • 2007
  • We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

DEMS와 H-terminated Si (001) 표면의 상호작용: 제일원리연구 (Interaction of DEMS with H-terminated Si (001) Surface: A First Principles Study)

  • 김대현;김대희;박소연;서화일;이도형;김영철
    • 한국세라믹학회지
    • /
    • 제46권4호
    • /
    • pp.425-428
    • /
    • 2009
  • We performed a density functional theory study to investigate the interaction of DEMS (diethoxymethylsilane) with the H-terminated Si (001) surface. The optimum structure of DEMS was first calculated by a first principles study. The dissociation probability of the O-C bond of DEMS was higher than the other seven bonds based on the bond energy calculation. When the fragmented DEMS groups reacted with the H-terminated Si (001) surface, it was the most favorable among the eight reactions to form a bond between the Si atom on the surface and the O atom of a fragmented DEMS group (($C_2H_5O$)Si($CH_3$)(H)-O-) by forming a $C_2H_6$ as by-product.

Charge Transport Properties of Boron/Nitrogen Binary Doped Graphene Nanoribbons: An ab Initio Study

  • Kim, Seong Sik;Kim, Han Seul;Kim, Hyo Seok;Kim, Yong Hoon
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
    • /
    • pp.180.2-180.2
    • /
    • 2014
  • Opening a bandgap by forming graphene nanoribbons (GNRs) and tailoring their properties via doping is a promising direction to achieve graphene-based advanced electronic devices. Applying a first-principles computational approach combining density functional theory (DFT) and DFT-based non-equilibrium Green's function (NEGF) calculation, we herein study the structural, electronic, and charge transport properties of boron-nitrogen binary edge doped GNRs and show that it can achieve novel doping effects that are absent for the single B or N doping. For the armchair GNRs, we find that the B-N edge co-doping almost perfectly recovers the conductance of pristine GNRs. For the zigzag GNRs, it is found to support spatially and energetically spin-polarized currents in the absence of magnetic electrodes or external gate fields: The spin-up (spin-down) currents along the B-N undoped edge and in the valence (conduction) band edge region. This may lead to a novel scheme of graphene band engineering and benefit the design of graphene-based spintronic devices.

  • PDF

Guest Changes Host: Adsorption Site and Binding Nature of Hydrogen in MOF-5

  • 주재용;김형준;한상수
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
    • /
    • pp.160.1-160.1
    • /
    • 2014
  • Using a density functional theory calculation including van der Waals (vdW) corrections, we report that $H_2$ adsorption in a cubic-crystalline microporous metal-organic framework (MOF-5) leads to volume shrinkage, which is in contrast to the intuition that gas adsorption in a confined system (e.g., pores in a material) increases the internal pressure and then leads to volumetric expansion. This extraordinary phenomenon is closely related to the vdW interactions between MOF and $H_2$ along with the $H_2$-$H_2$ interaction, rather than the Madelung-type electrostatic interaction. At low temperatures, $H_2$ molecules adsorbed in the MOF-5 form highly symmetrical interlinked nanocages that change from a cube-like shape to a sphere-like shape with $H_2$ loading, helping to exert centrosymmetric forces and hydrostatic (volumetric) stresses from the collection of dispersive interactions. The generated internal negative stress is sufficient to overcome the stiffness of the MOF-5 which is a soft material with a low bulk modulus (15.54 GPa).

  • PDF

Adsorption Configuration of Serine on Ge(100): Competition between the Hydroxymethyl and Carboxyl groups of Serine During the Adsorption Reaction

  • 김예원;양세나;이한길
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
    • /
    • pp.182-182
    • /
    • 2011
  • We investigated the adsorption structures of serine on a Ge(100) surface by core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. The core-level C 1s, N 1s, and O 1s CLPES spectra confirmed that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction, thereby favoring formation of the "O-H dissociated-N dative bonded" and "O-H dissociation bonded" structures at 0.30 ML and 0.60 ML, respectively. The experimental results were corroborated theoretically by calculating the reaction pathways leading to the two adsorption geometries. The reaction pathways indicated that the "O-H dissociated-N dative bonded structure" is the major product of serine adsorption on Ge(100) due to comparably stable adsorption energy.

  • PDF

Vibrational Analysis of Azacrown Ether Complex with Li Metal Cation

  • Min, Kyung-Chul;Park, Sun-Kyung;Lee, Choong-Keun;Kim, Chang-Suk;Lee, Nam-Soo
    • Bulletin of the Korean Chemical Society
    • /
    • 제31권11호
    • /
    • pp.3385-3390
    • /
    • 2010
  • $Li^+$ ion complex of azacrown ether with restricted motion of freedom and pseudo-bilateral symmetry was studied by infrared spectroscopy, which has shown simplified and broadened vibrational features. The C=O and N-H stretching bands, in particular, shows anomalous broadening nearly ${\sim}50\;cm^{-1}$. The density functional calculation at the level of BP86/6-31+$G^{**}$ shows that $Li^+$ ion is trapped and rather free to move around inside the cavity, as much as about $0.70\;{\AA}$. Through the relocation of $Li^+$ ion inside the cavity, the conformational changes would occur rapidly in its symmetry $C_1\;{\rightleftarrows}\;C_2\;{\rightleftarrows}\;C_1$$. The potential barrier was obtained to be merely ~2.2 kJ/mol for $C_1\;{\rightarrow}\;C_2$. During this conformational alteration, the amide backbone twists concurrently its dihedral angle side to side about up to ${\pm}3$ degree. Selected vibrational modes were interpreted in terms of the force constant variations of local symmetry coordinates between conformations in the framework of $C_1\;{\rightleftarrows}\;C_2\;{\rightleftarrows}\;C_1$.

A Two-dimensional Supramolecular Network Built through Unique π-πStacking: Synthesis and Characterization of [Cu(phen)2(μ-ID A)Cu(phen)·(NO3)](NO3)·4(H2O)

  • Lin, Jian-Guo;Qiu, Ling Qiu;Xu, Yan-Yan
    • Bulletin of the Korean Chemical Society
    • /
    • 제30권5호
    • /
    • pp.1021-1025
    • /
    • 2009
  • A novel supramolecular network containing binuclear copper unit $[Cu(phen)_{2}({\mu}-ID\;A)Cu(phen){\cdot}(NO_{3})](NO_{3}){\cdot}4(H_{2}O)$ (1) was synthesized through the self-assembly of iminodiacetic acid ($H_2IDA$) and 1,10-phenanthroline (phen) in the condition of pH = 6. It has been characterized by the infrared (IR) spectroscopy, elemental analysis, single crystal X-ray diffraction, and thermogravimetric analysis (TGA). 1 shows a 2-D supramolecular structure assembled through strong and unique $\pi-\pi$ packing interactions. Density functional theory (DFT) calculations show that theoretical optimized structures can well reproduce the experimental structure. The TGA and powder X-ray diffraction (PXRD) curves indicate that the complex 1 can maintain the structural integrity even at the loss of free water molecules. The magnetic property is also reported in this paper.

Comparative Studies on Two Fluoro-Substituted 2-Pyrazoline Derivatives with Experimental and Theoretical Methods

  • Guo, Huan-Mei;Wang, Xian;Jian, Fang Fang;Xiao, Hai Lian;Zhao, Pu Su
    • Bulletin of the Korean Chemical Society
    • /
    • 제30권5호
    • /
    • pp.1061-1066
    • /
    • 2009
  • Two fluoro-substituted 2-pyrazoline derivatives, 1-phenyl-3-(4-methoxyphenyl)-5-(4-fluorophenyl)-2-pyrazoline (1) and 1-phenyl-3-(4-methoxyphenyl)-5-(2-fluoro-phenyl)-2-pyrazoline (2) have been synthesized and characterized by elemental analysis, IR, UV-Vis and fluorescence spectra. The crystal structure of 1 has been determined by X-ray single crystal diffraction. For the two compounds, density functional theory (DFT) calculations of the structures and natural population atomic charge analysis (NPA) have been performed at B3LYP/6-311G** level of theory. By using TD-DFT method, electron spectra of 1 and 2 have been predicted, which are very approximate with the experimental ones. Comparative studies on 1 and 2 indicate that the location change of fluorine atom in 5-position phenyl ring of 2-pyrazoline does not make significant change of geometries and electronic transition bands, but it leads to evident change of atomic charge distributions and peak intensities of UV and fluorescence spectra.

Local Electronic Structures of Graphene Probed by Scanning Tunneling Spectroscopy

  • Jang, Won-Jun;Lee, Eui-Sup;Kim, Howon;Yoon, JongKeon;Chang, Yunhee;Kim, Yong-Hyun;Kahng, Se-Jong
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
    • /
    • pp.132.2-132.2
    • /
    • 2013
  • Electrons in graphene make ballistic transport with very high mobility (${\sim}2{\times}105 $cm2V-1s-1), which holds promises for applications in fast electronic devices. However, such expectations have been hampered by the semi-metallicity or zero bandgap of graphene, which makes it impossible to completely turn off graphene transistor devices. Here, we report the observations of local bandgap modulations in Moir$\acute{e}$ patterned graphene on metal substrates using scanning tunneling microscopy and spectroscopy. The Moir$\acute{e}$ patterned graphene was made by combinations of self-assembly processes, and they showed additional electronic states that could be interpreted as sub-band states. Our experimental observations could be explained with orbital transitions of carbon atoms from sp2 to sp3, as supported by our density functional theory calculation results. Our findings will add new poweful components for device applications.

  • PDF

플라즈마 보조 분자선 적층 성장법으로 성장한 ZnO 박막의 청색 발광 중심 (Blue Luminescent Center in Undoped ZnO Thin Films Grown by Plasma-assisted Molecular Beam Epitaxy)

  • 김종빈;노영수;변동진;박동희;최원국
    • 한국재료학회지
    • /
    • 제19권5호
    • /
    • pp.281-287
    • /
    • 2009
  • ZnO thin film was grown on a sapphire single crystal substrate by plasma assisted molecular beam epitaxy. In addition to near band edge (NBE) emissions, both blue and green luminescences are also observed together. The PL intensity of the blue luminescence (BL) range from 2.7 to 2.9 eV increased as the amount of activated oxygen increased, but green luminescence (GL) was weakly observed at about 2.4 eV without much change in intensity. This result is quite unlike previous studies in which BL and GL were regarded as the transition between shallow donor levels such as oxygen vacancy and interstitial zinc. Based on the transition level and formation energy of the ZnO intrinsic defects predicted through the first principle calculation, which employs density functional approximation (DFA) revised by local density approximation (LDA) and the LDA+U approach, the green and blue luminescence are nearly coincident with the transition from the conduction band to zinc vacancies of $V^{2-}_{Zn}$ and $V^-_{Zn}$, respectively.