井冈山大学学报（自然科学版）
井岡山大學學報（自然科學版）
정강산대학학보（자연과학판）
JOURNAL OF JINGGANGSHAN UNIVERSITY(SCIENCE AND TECHNOLOGY)
2013年
1期
39-47
,共9页
离子液体%密度泛函理论%2-甲基噻吩%正己烷%异丁基硫醇
離子液體%密度汎函理論%2-甲基噻吩%正己烷%異丁基硫醇
리자액체%밀도범함이론%2-갑기새분%정기완%이정기류순
ionic liquid%density functional theory%2-methyl-thiophene%hexane%isobutylthiol
采用密度泛函理论考察了1-乙基-3-甲基咪唑四氟合硼酸盐([EMIM][BF4])和2-甲基噻吩(2-MT)、正己烷(HEX)、异丁基硫醇(IBT)的相互作用.采用GGA/PW91和DNP基组优化了结构,并用NBO和AIM分析了[EMIM][BF4]和2-甲基噻吩(2-MT)、正己烷(HEX)、异丁基硫醇(IBT)的氢键相互作用.[EMIM][BF4]离子对最稳定的气相结构表明,[BF4]-阴离子的F原子和咪唑环上C2-H2的氢键作用在形成离子对中起重要作用.[BF4]-阴离子和[EMIM]+阳离子支链发生氢键作用.[BF4]-阴离子趋向于C2-H2形成氢键,这说明,2-甲基噻吩(2-MT)、正己烷(HEX)、异丁基硫醇(IBT)吸附在[EMIM][BF4]上没有改变离子液体离子对的主要作用.[EMIM][BF4]和2-甲基噻吩发生p···C-H 和氢键作用,而[EMIM][BF4]和正己烷(HEX)、异丁基硫醇(IBT)主要发生氢键作用.相互作用能表明,2-甲基噻吩优先吸附在离子液体上.
採用密度汎函理論攷察瞭1-乙基-3-甲基咪唑四氟閤硼痠鹽([EMIM][BF4])和2-甲基噻吩(2-MT)、正己烷(HEX)、異丁基硫醇(IBT)的相互作用.採用GGA/PW91和DNP基組優化瞭結構,併用NBO和AIM分析瞭[EMIM][BF4]和2-甲基噻吩(2-MT)、正己烷(HEX)、異丁基硫醇(IBT)的氫鍵相互作用.[EMIM][BF4]離子對最穩定的氣相結構錶明,[BF4]-陰離子的F原子和咪唑環上C2-H2的氫鍵作用在形成離子對中起重要作用.[BF4]-陰離子和[EMIM]+暘離子支鏈髮生氫鍵作用.[BF4]-陰離子趨嚮于C2-H2形成氫鍵,這說明,2-甲基噻吩(2-MT)、正己烷(HEX)、異丁基硫醇(IBT)吸附在[EMIM][BF4]上沒有改變離子液體離子對的主要作用.[EMIM][BF4]和2-甲基噻吩髮生p···C-H 和氫鍵作用,而[EMIM][BF4]和正己烷(HEX)、異丁基硫醇(IBT)主要髮生氫鍵作用.相互作用能錶明,2-甲基噻吩優先吸附在離子液體上.
채용밀도범함이론고찰료1-을기-3-갑기미서사불합붕산염([EMIM][BF4])화2-갑기새분(2-MT)、정기완(HEX)、이정기류순(IBT)적상호작용.채용GGA/PW91화DNP기조우화료결구,병용NBO화AIM분석료[EMIM][BF4]화2-갑기새분(2-MT)、정기완(HEX)、이정기류순(IBT)적경건상호작용.[EMIM][BF4]리자대최은정적기상결구표명,[BF4]-음리자적F원자화미서배상C2-H2적경건작용재형성리자대중기중요작용.[BF4]-음리자화[EMIM]+양리자지련발생경건작용.[BF4]-음리자추향우C2-H2형성경건,저설명,2-갑기새분(2-MT)、정기완(HEX)、이정기류순(IBT)흡부재[EMIM][BF4]상몰유개변리자액체리자대적주요작용.[EMIM][BF4]화2-갑기새분발생p···C-H 화경건작용,이[EMIM][BF4]화정기완(HEX)、이정기류순(IBT)주요발생경건작용.상호작용능표명,2-갑기새분우선흡부재리자액체상.
Density functional theory has been employed to investigate the interaction between 2-methyl-thiophene (2-MT), hexane (HEX), isobutylthiol (IBT) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]). GGA/PW91 functionals and DNP basis set were used to optimize the geometries, and the hydrogen bond interaction between [EMIM][BF4] and 2-methyl-thiophene (2-MT), hexane (HEX), isobutylthiol (IBT) have been analyzed by NBO and AIM methods. The most stable gas-phase structure of [EMIM][BF4] ion pair indicates that hydrogen bond interaction between the fluorine atoms on [BF4]- anions and the C2-hydrogen on the imidazole ring plays an important role in the formation of ion pair. Additional interaction is observed between [BF4]-anion and the hydrogen atoms on the adjacent alkyl side chains of [EMIM]+cation. The [BF4]-anion tends to C2-H2 forming hydrogen bond, suggesting that 2-methyl-thiophene (2-MT), hexane (HEX), isobutylthiol (IBT)’s adsorption on [EMIM][BF4] do not change the dominant role of ionic liquids pair. Thep···C-H interaction and hydrogen bonding interaction occur between [EMIM][BF4] and 2-methyl-thiophene. The hydrogen bonding interaction exists between [EMIM][BF4] and hexane, isobutylthiol. The interaction energy suggests that 2-methyl-thiophene is prior to adsorpt on ionic liquids.
