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4. „µ¦ª· Á‡¦µ³®ro°¤¼¨ ¨³‡»–¤´˜·˜nµŠ Ç Ã‡¦Š¦oµŠš¸Éŗo‹µ„„µ¦‡Î µœª– ‹³œÎµ¤µª·Á‡¦µ³®r™¹Š‡ªµ¤
Áž}œÅžÅ—oĜ„µ¦Á„·—„µ¦—¼—Ž´¦³®ªnµŠÃ‡¦Š¦oµŠ °Š˜´ª—¼—Ž´ (µ¦ž¦³„°Â°¤Ã¤Áœ¸¥) ×¥¡·‹µ¦–µ‡ªµ¤¥µª
¡´ œ›³ ¨³¤»¤ š¸ÉÁž¨¸É¥œÂž¨ŠÅž¦nª¤„´„µ¦¡· ‹µ¦–µ¡¨´ŠŠµœ °Š¦³Å—oץčo ¤„µ¦ (Dapprich et al. 1999 :
461-462) ) ( Re
2
Cluster
Low
Cluster
High
al
LOW ONNIOM E E E E
Ÿ¨„µ¦ª·‹´¥Â¨³°£·ž¦µ¥Ÿ¨
Ÿ¨„µ¦‡Îµœª– ¨´„µ¦ª·Á‡¦µ´®ro°¤¼ ¨
„µ¦Á„·—°´œ˜¦„·¦·¥µ °ŠÂ°Ã¤Áœ¸¥œÃ‡¦Š¦oµŠŽ¸Ã°Å¨˜rœ·— H-ZSM-5 ×¥Áž¦¸ ¥Áš¸¥Ÿ¨ °Š¦³Á¸¥
ª·›¸ „µ¦ HF „´ DFT(B3LYP) ץčo basis set 6-31G(d,p)
„µ¦—¼—Ž´ µ¦ž¦³„°Â°¤Ã¤Áœ¸¥œ H-ZSM-5 Ž¸Ã°Å¨˜r
1. °´œ˜¦„·¦·¥µ¦³®ªnµŠ [NH3]/[H-ZSM-5], 5T-quantum cluster : HF/6-31G(d,p) ¨³
B3LYP/6-31G(d,p)
HF/6-31g(d,p B3LYP/6-31g(d,p)
Total energy = -1761.17 a.u. Total energy = -1766.04 a.u.
Binding energy = -16.18 kcal/mol Binding energy = -17.06 kcal/mol
‹µ„ǦŠ¦o µŠÂ—Š°´œ˜¦„·¦·¥µ¦³®ªnµŠ NH3 „´ H-ZSM-5 zeolite; 5T cluster ¡¨´ ŠŠµœš¸Éŗo ‹µ„„µ¦
‡Îµœª–—o ª¥¦³Á¸¥ª·›¸ HF/6-31G(d,p), B3LYP/6-31G(d,p) ¤¸‡nµ¡¨´ŠŠµœ °Š¦³ [NH3]/[H-ZSM-5];5T cluster
Ášnµ„´ -1761.17 a.u., -1766.04 a.u. ¡¨´ŠŠµœ„µ¦—¼—Ž´(adsorption energy) Ášnµ„´ -16.18 kcal/mol, -17.06 kcal/mol
˜µ¤¨Î µ—´ ¨³¦·Áª–š¸É Á„·—ž’·„·¦·¥µ‡º°¦·Áª–°³˜°¤ÅœÃ˜¦Á‹œ (N) °ŠÂ°¤Ã¤Áœ¸ ¥„´°³˜°¤Å±Ã—¦Á‹œ (Hz)
°ŠŽ¸Ã°Å¨˜r¤¸‡ªµ¤¥µª¡´œ›³ N-Hz Ášnµ„´ 1.68 Å, 1.10 Š¨³°³˜°¤°°„Ž·Á‹œš¸É 2 (O2) °ŠŽ¸Ã°Å¨˜r „´°³˜°¤
űצÁ‹œ (H) °ŠÂ°¤Ã¤Áœ¸¥¤¸‡ªµ¤¥µª¡´œ›³ O2-H Ášnµ„´ 2.41 Å, 1.65 Å ˜µ¤¨Îµ—´