Ï°Ìâ4
4-1 ±È½Ï¼Û¼üÀíÂÛÓë·Ö×Ó¹ìµÀÀíÂÛ´¦ÀíH2ÌåϵµÄÒìͬµã¡£
22c1Haa?2c1c2Hab?c2Hbb????4.2. ¶ÔH2Ìåϵ£¬¸ù¾Ý¼«ÖµÌõ¼þ£ºµ¼?0£¬?0ÒÔ¼°??22?c1?c2c1Saa?2c1c2Sab?c2Sbb+
³ö c1(Haa?ESaa)?c2(Hab?ESab)?0 c1(Hab?ESab)?c2(Hbb?ESbb)?0
4.3¡¢±È½ÏO2+¡¢O2 ¡¢O2 ¡¢O22 µÄ¼ü³¤¼°´ÅÐÔ£¬²¢°´Ë³ÐòÅÅÁС£
£
£
4.4. °´·Ö×Ó¹ìµÀÀíÂÛ˵Ã÷Cl2µÄ»¯Ñ§¼ü±ÈCl2+Ç¿»¹ÊÇÈõ£¿ÎªÊ²Ã´£¿
4-5 ¸ù¾ÝN2+¡¢N2¡¢N2- µÄµç×Ó×é̬£¬Ô¤²â¸÷ÌåϵN-N¼ü³¤¶È£¬²¢±È½ÏËüÃǵÄÎȶ¨ÐÔ¡£ 4.6¡¢ÓÃÁ½ÖÖ·Ö×Ó¹ìµÀ¼ÇºÅд³öO2µÄ·Ö×Ó¹ìµÀ£¬²¢»³ö¹ìµÀÄܼ¶Í¼¡£ 4-7¡¢CFºÍCF+ÄÄÒ»¸öµÄ¼ü³¤¶ÌЩ£¿
4.8¡¢»³öCNµÄ·Ö×Ó¹ìµÀÄܼ¶Ê¾Òâͼ£¬Ð´³ö»ù̬µÄµç×Ó×é̬£¬¼ÆËã¼ü¼¶¼°²»³É¶Ôµç×ÓÊý¡£ 4.9¡¢ÊÔÓ÷Ö×Ó¹ìµÀÀíÂÛÌÖÂÛSO·Ö×ӵĵç×ӽṹ£¬ËµÃ÷»ù̬ʱÓм¸¸ö²»³É¶Ôµç×Ó.
4.10¡¢ÏÂÁÐABÐÍ·Ö×Ó£º NO ¡¢O2 ¡¢C2 ¡¢CN¡¢COÄļ¸¸öÊǵõç×Ó±äΪABºó±ÈÔÀ´ÖÐ
ÐÔ·Ö×ÓÄÜÁ¿µÍ£¬Äļ¸¸öÊÇʧµç×Ó±äΪAB+ºó±ÈÔÀ´ÖÐÐÔ·Ö×ÓÄÜÁ¿µÍ£¿ 4.11¡¢OH·Ö×ÓÒÑÔÚÐǼʿռ䷢ÏÖ
1£©ÊÔ°´·Ö×Ó¹ìµÀÀíÂÛÖ»ÓÃÑõÔ×Ó2p¹ìµÀºÍÇâÔ×ÓµÄ1s¹ìµÀµþ¼Ó£¬Ð´³öÆäµç×Ó×é̬¡£ 2£©ÔÚÄĸö·Ö×Ó¹ìµÀÖÐÓв»³É¶Ôµç×Ó£¿
3£©´Ë¹ìµÀÊÇÓÉÑõºÍÇâµÄÔ×Ó¹ìµÀµþ¼ÓÐγɣ¬»¹ÊÇ»ù±¾É϶¨ÓòÓÚij¸öÔ×ÓÉÏ£¿
4£©ÒÑÖªOHµÄµÚÒ»µçÀëÄÜΪ13.2eV¡¢HFΪ16.05eV£¬ËüÃǵIJîÖµ¼¸ºõºÍOÔ×ÓÓëFÔ×ӵĵÚÒ»µçÀëÄÜ£¨15.8eVºÍ18.6eV£©µÄ²îÖµÏàͬ£¬ÎªÊ²Ã´£¿
4.12¡¢¶ÔÓÚH2+»òÆäËüͬºËË«Ô×Ó·Ö×Ó£¬²ÉÓÃca?A?cb?BΪ·Ö×Ó¹ìµÀʱ£¬ÇÒ?A¡¢?B¾ùΪ
1s»ò2s¹ìµÀ£¬½ö½öͨ¹ý±ä·Ö¼ÆËã¶ø²»ÇóÖúÓÚ¶Ô³ÆÐÔÔÀí£¬ÄãÄÜÍƳöca??cbÂ𣿠4.13¡¢ÒÔZÖáΪ¼üÖᣬ°´¶Ô³ÆÐÔÆ¥ÅäÔÔò£¬ÏÂÁи÷¶ÔÔ×Ó¹ìµÀÄÜ·ñ×é³É·Ö×Ó¹ìµÀ£¬ÈôÄÜÐγÉ
д³ö·Ö×Ó¹ìµÀµÄÀàÐÍ¡£
¢Ù s dz2 ¢Ú dxy dxy ¢Û dyz dyz ¢Ü s dxy 4.14¡¢ÏÂÁзÖ×Ó¿ÉÄܾßÓе¥µç×ӦмüµÄÊÇ
¢Ù N2+ ¢Ú C2 ¢Û B2+ ¢Ü O2
£
£
£
£
4.15¡¢±È½ÏÏÂÁзÖ×Ӵžأ¬²¢°´´óС˳ÐòÅÅÁУº Li2 C2 C2+ B2 4.16¡¢Br2·Ö×ÓµÄ×îµÍ¿Õ¹ìµÀ£¨LUMO£©ÊÇ ¢Ù
**?4p ¢Ü ?4p ?4? ¢Ú pZ4pZ ¢Ûxz*4.17¡¢COµÄ¼ü³¤Îª112.9pm£¬CO+µÄ¼ü³¤Îª111.5pm£¬ÊÔ½âÊÍÆäÔÒò¡£ 4.18¡¢ÊÔ´ÓË«Ô×Ó·Ö×Ó¹ìµÀµÄÄܼ¶½âÊÍ£º
9
¢ÅN2µÄ¼üÄܱÈN2+´ó£¬¶øO2µÄС¡£
¢ÆNOµÄ¼üÄܱÈNO+µÄС¼°ËüÃÇ´ÅÐԵIJî±ð¡£
4.19¡¢ÊÔ´ÓMOÀíÂÛд³öË«Ô×Ó·Ö×ÓOF¡¢OF¡¢OF+µÄµç×Ó¹¹ÐÍ£¬ÇóËüÃǵļü¼¶£¬²¢½âÊÍËü
£
Ãǵļü³¤¡¢¼üÄܺʹÅÐԵı仯¹æÂÉ¡£
4.20¡¢ÏÖÓÐ4S£¬4Px£¬4Py£¬3dz2£¬3dx2?y2£¬3dxy£¬3dxz£¬3dyzµÈ9¸öÔ×Ó¹ìµÀ£¬Èô¹æ¶¨
ZÖáΪ¼üÖá·½Ïò£¬ÔòËüÃÇÖ®¼ä£¨°üÀ¨×ÔÉí¼ä£©¿ÉÄÜ×é³ÉÄÄЩ·Ö×Ó¹ìµÀ£¿¸÷ÊǺÎÖÖ·Ö×Ó¹ìµÀ¡£
4.21¡¢Çëд³öCl2¡¢O2+ºÍCN»ù̬ʱ¼Û²ãµÄ·Ö×Ó¹ìµÀ±í´ïʽ£¬²¢ËµÃ÷ÊÇ˳´ÅÐÔ»¹ÊÇ·´´ÅÐÔ¡£
£
4.22¡¢HF·Ö×ÓÒÔºÎÖÖ¼ü½áºÏ£¿Ð´³öÕâÖÖ¼üµÄÍêÈ«²¨º¯Êý¡£ 4-23¡¢·Ö±ðÓÃMOÓëVB·½·¨·ÖÎöCO¡¢BN¡¢NOµÄ»¯Ñ§¼ü¡£
4-24¡¢ÊµÑé²â¶¨Â±ËØ·Ö×Ó¼°¸ºÀë×ÓµÄƽºâ¼ü¾à¡¢Õñ¶¯²¨ÊýÓë½âÀëÄÜΪ£º
F2 F2-
re (pm)
1.411 1.900
?(cm-1) 916.6 450.0
De(eV) 1.60 1.31
ÊÔ´Ó·Ö×ӵĵç×Ó×é̬˵Ã÷ÕâЩÊý¾Ý
4.25ÈôABÐÍ·Ö×ÓµÄÔ×ÓAºÍBµÄ¿âÂØ»ý·Ö·Ö±ðΪHAAºÍHBB£¬ÇÒHAA>HBB, ²¢ÉèSAB~0£¨¼´
ºöÂÔÈ¥SAB£©ÊÔÖ¤Ã÷³É¼üµÄMOµÄÄܼ¶ºÍ·´¼üµÄMOµÄÄܼ¶·Ö±ðΪ£º E³É£½HBB2HAB? HBB?HAAE·´£½HAA
4.26¡¢ÊÔд³öÔÚ¼Û¼üÀíÂÛÖÐÃèÊöH2Ô˶¯×´Ì¬µÄ·ûºÏPauliÔÀíµÄ²¨º¯Êý£¬²¢Çø·Öµ¥Ì¬ºÍÈýÖØ
̬¡£
2HAB?HAA?HBB
V1?V2e24-27¡¢H2³É¼ü¹ìµÀÄÜÁ¿ÇúÏß¿ÉÓÃÏÂʽ±íʾ£º E?EH?£¬ÆäÖÐV1ÊÇÒ»ºË?1?S4??0R+
µç×ÓÖÐÐÄÓëÁíÒ»ºËµçºÉ¼äµÄÎüÒýÄÜ£¬V2ÊǺËÓëµçºÉÖصþÃܶȼäµÄÎüÒýÄÜ£¬¸ù¾ÝϱíÊý¾Ý»³ö·Ö×ӳɼü¹ìµÀÊÆÄÜÇúÏߣ¬Ñ°ÕÒƽºâ¼ü³¤Óë¼ü½âÀëÄÜ¡£ R£¨a0£© V1(Eh) V2(Eh) S 0 1.00 1.00 1.00 1 0.729 0.736 0.858 2 0.473 0.406 0.587 3 0.330 0.199 0.349 4 0.250 0.092 0.189 Eh=27.3eV, a0=52.9pm, EH=-1/2Eh
V1?V2e24-28 ÉÏÌâÊý¾ÝÒ²¿ÉÓÃÀ´¼ÆËã·´¼ü¹ìµÀÊÆÄÜÇúÏߣ¬E?EH? ?1?S4??0R
10
Ï°Ìâ5
5.1ÊÔд³ösp3ÔÓ»¯¹ìµÀµÄ±í´ïÐÎʽ¡£
5.2.´ÓÔ×Ó¹ìµÀ?sºÍ?pµÄÕý½»ÐÔ£¬Ö¤Ã÷Á½¸öspÔÓ»¯¹ìµÀÏ໥Õý½»¡£
x h1???s?1???px h2?1???s???px
5.3д³öÏÂÁзÖ×Ó»òÀë×ÓÖУ¬ÖÐÐÄÔ×ÓËù²ÉÓõÄÔÓ»¯¹ìµÀ£º
CS2£¬NO2+£¬NO3£¬CO32£¬BF3£¬CBr4£¬PF4+£¬IF6+
£
£
5.4.ÊÔÇóµÈÐÔd2sp3ÔÓ»¯¹ìµÀµÄ²¨º¯ÊýÐÎʽ¡£
5.5 ÊÔÓÃÔÓ»¯¹ìµÀÀíÂÛ˵Ã÷NO£¬NO2£¬N2OµÄ»¯Ñ§¼ü¡£
5.6 ʵÑé²â¶¨Ë®·Ö×ÓµÄ?HOHΪ104.5?, ÊÔ¼ÆËãO-H¼üÓë¹Â¶Ôµç×ÓÔÓ»¯¹ìµÀÖÐs¡¢p¹ìµÀµÄ³É·Ö¡£
5.7 Óü۵ç×Ó¶Ô»¥³âÀíÂÛ½âÊÍÏÂÁзÖ×ӼнDZ仯 £¨1£©NH3(107.3?), PH3(93.3?) , AsH3(91.8?);
(2) H2O(104.5?), H2S(92.2?), H2Se(91.0?), H2Te(89.5?).
5.8.ʹÓÃVSEPRÄ£ÐÍ£¬¶ÔÏÂÃæ¸ø³öijЩNºÍPµÄÇ⻯ÎïºÍ·ú»¯ÎïµÄ¼ü½Ç×ö³ö½âÊÍ
NH3 PH3
107 94
£
¡ð¡ð
NF3 PF3
102 104
¡ð
¡ð
5.9.ÒÀVSEPRÀíÂÛÔ¤²âSCl3+ºÍICl4µÄ¼¸ºÎ¹¹ÐÍ£¬¸ø³ö¸÷×ÔÇé¿öÏÂÖÐÐÄÔ×ÓµÄÑõ»¯Ì¬ºÍÔÓ»¯·½Ê½¡£
5.10.¶ÔÏÂÁзÖ×ÓºÍÀë×ÓCO2£¬NO2+£¬NO2£¬NO2£¬SO2£¬ClO2£¬O3µÈ£¬ÅжÏËüÃǵÄÐÎ×´£¬Ö¸
£
³öÖÐÐÔ·Ö×ӵļ«ÐÔ£¬Ö¸³öÿ¸ö·Ö×ÓºÍÀë×ӵIJ»³É¶Ôµç×ÓÊý¡£
5.11.ÀûÓü۵ç×Ó¶Ô»¥³âÀíÂÛ˵Ã÷AsH3, ClF3, SO3, SO32,CH3+,CH3,ICl3µÈ·Ö×ÓºÍÀë×ӵļ¸ºÎ
£
£
ÐÎ×´£¬ËµÃ÷ÄÇЩ·Ö×ÓÓÐż¼«¾Ø¡£
5.12.¶ÔÓÚ¼«ÐÔ·Ö×ÓAB£¬Èç¹û·Ö×Ó¹ìµÀÖеÄÒ»¸öµç×ÓÓÐ90£¥µÄʱ¼äÔÚAµÄÔ×Ó¹ìµÀ?AÉÏ£¬
10£¥µÄʱ¼äÔÚBµÄÔ×Ó¹ìµÀ?BÉÏ£¬ÊÔÃèÊö¸Ã·Ö×Ó¹ìµÀ²¨º¯ÊýµÄÐÎʽ£¨´Ë´¦²»¿¼ÂÇÔ×Ó¹ìµÀµÄÖصþ£©
5.13.ÓÃÔÓ»¯¹ìµÀÀíÂÛÌÖÂÛÏÂÁзÖ×ӵļ¸ºÎ¹¹ÐÍ£º
C2H2£¬BF3£¬NF3£¬C6H6£¬SO3
5.14.ÌÖÂÛÏÂÁзÖ×ÓºÍÀë×ÓÖеĻ¯Ñ§¼ü¼°¼¸ºÎ¹¹ÐÍ£º
CO2£¬H2S£¬PCl3£¬CO32£¬NO3£¬SO42
£
£
£
11
5.15ÅжÏÏÂÁзÖ×ÓÊÇ·ñÐγɴó? ¼ü£¬ ÈôÓÐÇëд³ö?mn£ºCH?C-CH2-CH3, C6H6-CH=CH2, C6H5Cl , CH2=C=O , NO2
¡ª¡ª
5.16.±È½ÏROH£¬C6H5OH£¬RCOOHµÄËáÐÔ£¬²¢ËµÃ÷ÆäÀíÓÉ¡£ 5.17ÊԱȽÏCO£¬R-COH£¬CO2̼Ñõ¼ä¼ü³¤µÄ´óС£¬ÎªÊ²Ã´£¿
5.18.»·¼ºÍ顪1£¬4¶þͪÓÐÎåÖÖ¿ÉÄܹ¹Ïó£ºÒÎʽ£¬Á½ÖÖ´¬Ê½£¬Á½ÖÖŤתʽ£¨¶Ô³ÆÐÔÒ»¸ßÒ»µÍ£©¡£Ç뻳öÕâÎåÖÖ¹¹Ï󣬲¢È·¶¨ËüÃÇËùÊôµÄµãȺ¡£
5.19.XeOnFm»¯ºÏÎïÊÇÎȶ¨µÄ£¨n£¬m=1£¬2£¬3¡£©£¬ÇëÓÃVSEPRÄ£ÐÍ£¬ÍƵ¼ËùÓоßÓÐÕâһͨ
ʽµÄ»¯ºÏÎï½á¹¹¡£
5.20´ó²¿·ÖÎåÅäλ»¯ºÏÎï²ÉÓÃÈý½Ç˫׶»òËÄ·½×¶½á¹¹£¬Çë½âÊÍ£º
(1)µ±ÖÐÐÄÔ×ÓΪÖ÷×åÔªËØʱ£¬ÔÚÈý½Ç˫׶½á¹¹ÖÐÖáÏò¼ü±Èˮƽ¼ü³¤£¬¶øÔÚËÄ·½×¶ÖÐÔòÏà·´¡£
3-(2)µ±ÖÐÐÄÔ×ÓΪ¹ý¶É½ðÊôʱ£¬ÈçËÄ·½×¶[Ni£¨CN£©ÖáÏòNi¡ªC¼ü217pm£¬Ë®Æ½187pm£»5]ÖУ¬
¶øÔÚÈý½Ç˫׶ [CuCl5]3-ÖУ¬ÖáÏò¼üCu¡ªCl 230pm£¬Ë®Æ½¼ü239pm¡£ 5.21 ¸ù¾ÝH?ckel ½üËÆ£¬Ð´³öÏÂÁзÖ×ӦРµç×Ó·Ö×Ó¹ìµÀ¾ÃÆÚÐÐÁÐʽ£º
? ? ? ?
5.22.д³öÏÂÁи÷·Ö×ÓµÄÐݿ˶ûÐÐÁÐʽ£º
? ¢Ç C6H6 ¢Å CH2=CH2 ¢Æ CH2?CH?CH25.23 ÓÃHMO´¦Àí»·±ûÏ©×ÔÓÉ»ù£¬¼ÆËã? µç×ÓÄÜÁ¿Óë¹ìµÀ¡£
5.24.ÓÃHMO»òÏȶ¨ÏµÊý·¨Çó³öÎì¶þÏ©»ùÒõÀë×Ӧеç×Ó·Ö×Ó¹ìµÀµÄ±í´ïÐÎʽ¼°Æä¶ÔÓ¦µÄÄÜ
Á¿¡£
5.25.ÓÃHMO»òÏȶ¨ÏµÊý·¨Çó³öC6H6¦Ðµç×Ó·Ö×Ó¹ìµÀµÄ±í´ïÐÎʽ¼°Æä¶ÔÓ¦µÄÄÜÁ¿¡£ 5.26ÊÔÇó±½°··Ö×ÓµÄ? µç×Ó·Ö×Óͼ¡£ 5.27 ¸»Ï©
3¸öÄÜÁ¿½ÏµÍµÄ? ¹ìµÀÊÇ£º
?1?0.24?71? ?2?0.5?(1?0.5?2?230.?432?9?(6? )?0.38?5 (4?5) )?2??4??5 ?3?0.602?(3??6?) 0.3?742?(?5) ¼ÆËã¸÷¸öCÔ×ӵĵçºÉÃܶȺÍCÔ×Ó¼äµÄ? µç×Ó¼ü¼¶¡£
5.28.ÊÔÓÃÇ°Ïß¹ìµÀÀíÂÛ˵Ã÷ÒÒÏ©ÔÚ¹âÕÕµÄÌõ¼þÏ£¬·¢Éú¶þ¾Û·´Ó¦Éú³É»·¶¡ÍéµÄ»úÀí¡£ 5.29.ÊÔÓÃÇ°Ïß¹ìµÀÀíÂÛ˵Ã÷·´Ó¦£ºC2H4?Br2? ??CH2Br?CH2Br²»¿ÉÄÜÊÇ»ùÔª·´Ó¦¡£
12