расчетная работа 1
.pdf
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
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Ɋɚɫɱɟɬɧɚɹ ɪɚɛɨɬɚ ʋ1
«ɇȿɗɆɉɂɊɂɑȿɋɄɂɃ ɄȼȺɇɌɈȼɈ-ɏɂɆɂɑȿɋɄɂɃ ɊȺɋɑȿɌ ɆɈɅȿɄɍɅɕ»
ȼ ɥɚɛɨɪɚɬɨɪɧɨɣ ɪɚɛɨɬɟ N1 ɩɪɟɞɥɚɝɚɟɬɫɹ ɩɪɨɜɟɫɬɢ ɫ ɩɨɦɨɳɶɸ ɩɪɨɝɪɚɦɦɧɨɝɨ ɤɨɦɩɥɟɤɫɚ GAMESS ɧɟɷɦɩɢɪɢɱɟ-
ɫɤɢɣ ɤɜɚɧɬɨɜɨ-ɯɢɦɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɦɨɥɟɤɭɥɵ, ɜɵɛɢɪɚɟɦɨɣ ɢɡ ɫɩɢɫɤɚ ɦɨɥɟɤɭɥ, ɧɚɢɛɨɥɟɟ ɢɧɬɟɪɟɫɧɵɯ ɫ ɬɨɱɤɢ ɡɪɟɧɢɹ ɫɩɟɰɢɚɥɢɡɚɰɢɢ ɫɬɭɞɟɧɬɚ.
ɉɨɞɝɨɬɨɜɤɚ ɜɯɨɞɧɵɯ ɞɚɧɧɵɯ ɞɥɹ ɪɚɫɱɟɬɚ ɩɨ ɩɪɨɝɪɚɦɦɟ GAMESS
(General Atomic and Molecular Electronic Structure System)
Ⱦɥɹ ɩɨɞɝɨɬɨɜɤɢ ɜɯɨɞɧɵɯ ɞɚɧɧɵɯ ɧɟɨɛɯɨɞɢɦɨ ɫɨɡɞɚɬɶ ɮɚɣɥ ɫ ɪɚɫɲɢɪɟɧɢɟɦ inp (ɢɦɹ.inp).
1. ɉɪɢɦɟɪ ɡɚɞɚɧɢɹ:
Ɏɚɣɥ clcf3.inp, ɫɨɞɟɪɠɚɳɢɣ ɜɯɨɞɧɵɟ ɞɚɧɧɵɟ ɞɥɹ ɨɩɬɢɦɢɡɚɰɢɢ ɝɟɨɦɟɬɪɢɢ ɢ ɦɢɧɢɦɢɡɚɰɢɢ ɩɨɥɧɨɣ ɷɧɟɪɝɢɢ ɦɨɥɟɤɭɥɵ CClF3 (ɬɨɱɟɱɧɚɹ ɝɪɭɩɩɚ ɫɢɦɦɟɬɪɢɢ C3v) ɜ ɛɚɡɢɫɟ 6-31G*.
$CONTRL SCFTYP=RHF RUNTYP=OPTIMIZE COORD=ZMT NPRINT=9 $END
$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END $DATA
ClCF3
CNV 3
1Cl
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1.7896 |
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aClCF |
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rCF |
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rCF |
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aClCF |
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rCF |
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aClCF |
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rCF=1.3474 |
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3 F |
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aClCF=110.378 |
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tClCFF=120.0 |
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$END |
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1 Cl
2C
F 5
4F
Ʉɨɦɦɟɧɬɚɪɢɣ
Ʉɨɦɚɧɞɵ ɜ ɮɚɣɥɟ ɢɦɹ.inp ɪɚɡɛɢɬɵ ɧɚ 3 ɝɪɭɩɩɵ. Ʉɚɠɞɚɹ ɝɪɭɩɩɚ ɧɚɱɢɧɚɟɬɫɹ ɫ ɧɚɡɜɚɧɢɹ ($CONTRL, $BASIS, $DATA) ɢ ɡɚɤɚɧɱɢɜɚɟɬɫɹ ɤɨɦɚɧɞɨɣ $END. ɉɨɪɹɞɨɤ ɡɚɞɚɧɢɹ ɝɪɭɩɩ ɤɨɦɚɧɞ ɢ ɤɨɦɚɧɞ ɜ ɧɢɯ ɢɡɦɟɧɟɧɢɸ ɧɟ ɩɨɞɥɟɠɢɬ. 1 ɫɬɪɨɤɚ – 1-ɹ ɝɪɭɩɩɚ; 2 ɫɬɪɨɤɚ – 2-ɹ ɝɪɭɩɩɚ; ɨɬ $DATA ɞɨ $END – 3-ɹ ɝɪɭɩɩɚ.
1 ɝɪɭɩɩɚ ɤɨɦɚɧɞ - $CONTRL
ɜɤɥɸɱɚɟɬ ɫɥɟɞɭɸɳɢɟ ɤɨɦɚɧɞɵ:
SCFTYP=RHF – ɪɚɫɱɟɬ ɨɝɪɚɧɢɱɟɧɧɵɦ ɦɟɬɨɞɨɦ ɏɚɪɬɪɢ-Ɏɨɤɚ,
SCFTYP =UHF – ɪɚɫɱɟɬ ɧɟɨɝɪɚɧɢɱɟɧɧɵɦ ɦɟɬɨɞɨɦ ɏɚɪɬɪɢ-Ɏɨɤɚ.
¾RUNTYP = OPTIMIZE – ɨɩɬɢɦɢɡɚɰɢɹ ɝɟɨɦɟɬɪɢɢ ɪɚɫɫɱɢɬɵɜɚɟɦɨɣ ɦɨɥɟɤɭɥɵ,
¾RUNTYP =ENERGY - ɦɢɧɢɦɢɡɚɰɢɹ ɷɧɟɪɝɢɢ,
ICHARG=0 ɢɥɢ 1, ɢɥɢ -1 ɢ ɬ.ɞ. - ɡɚɪɹɞ ɫɢɫɬɟɦɵ. ȿɫɥɢ ICHARG=0, ɬɨ ɷɬɭ ɤɨɦɚɧɞɭ ɦɨɠɧɨ ɩɪɨɩɭɫɬɢɬɶ.
x MULT=1 – ɫɢɧɝɥɟɬ ɢɥɢ 2 – ɞɭɛɥɟɬ, ɢɥɢ 3 – ɬɪɢɩɥɟɬ ɢ ɬ.ɞ. - ɦɭɥɶɬɢɩɥɟɬɧɨɫɬɶ ɷɥɟɤɬɪɨɧɧɨɝɨ ɫɨɫɬɨɹɧɢɹ. ȿɫɥɢ MULT=1, ɬɨ ɷɬɭ ɤɨɦɚɧɞɭ ɦɨɠɧɨ ɩɪɨɩɭɫɬɢɬɶ.
i COORD=ZMT – Z-ɦɚɬɪɢɰɚ ɞɥɢɧ ɫɜɹɡɟɣ, ɜɚɥɟɧɬɧɵɯ ɢ ɞɜɭɝɪɚɧɧɵɯ ɭɝɥɨɜ
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
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i COORD=CART – ɞɟɤɚɪɬɨɜɵ ɤɨɨɪɞɢɧɚɬɵ - ɫɩɨɫɨɛɵ ɜɵɛɨɪɚ ɫɢɫɬɟɦɵ ɤɨɨɪɞɢɧɚɬ ɜ ɤɨɦɚɧɞɧɨɣ ɝɪɭɩɩɟ $DATA (ɫɦ. ɧɢɠɟ) COORD=CART – ɞɟɤɚɪɬɨɜɵ ɤɨɨɪɞɢɧɚɬɵ
i NPRINT=7 – ɫɬɚɧɞɚɪɬɧɵɣ ɜɵɜɨɞ,
NPRINT=9 – ɜɵɜɨɞ ɧɚ ɩɟɱɚɬɶ ɦɚɬɪɢɰɵ ɡɚɪɹɞɨɜ ɢ ɩɨɪɹɞɤɨɜ ɫɜɹɡɟɣ.
2 ɝɪɭɩɩɚ ɤɨɦɚɧɞ - $BASIS
ɜɤɥɸɱɚɟɬ ɤɨɦɚɧɞɵ, ɨɩɪɟɞɟɥɹɸɳɢɟ ɜɵɛɨɪ ɨɞɧɨɝɨ ɢɡ ɫɬɚɧɞɚɪɬɧɵɯ ɛɚɡɢɫɧɵɯ ɧɚɛɨɪɨɜ ɞɥɹ ɧɟɷɦɩɢɪɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɢɥɢ ɦɟɬɨɞ ɩɨɥɭɷɦɩɢɪɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ:
GBASIS=STO – ɦɢɧɢɦɚɥɶɧɵɣ ɛɚɡɢɫɧɵɣ ɧɚɛɨɪ STO-NG,
=N21 |
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ɜɚɥɟɧɬɧɨ-ɪɚɫɳɟɩɥɟɧɧɵɣ ɛɚɡɢɫ N21-G, |
=N31 |
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ɜɚɥɟɧɬɧɨ-ɪɚɫɳɟɩɥɟɧɧɵɣ ɛɚɡɢɫ N31-G, |
=N311 - |
ɜɚɥɟɧɬɧɨ-ɪɚɫɳɟɩɥɟɧɧɵɣ ɛɚɡɢɫ N311-G, |
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=MNDO – ɦɢɧɢɦɚɥɶɧɵɣ ɛɚɡɢɫ Ʌɟɜɞɢɧɚ ɞɥɹ ɪɚɫɱɟɬɚ ɩɨ ɦɟɬɨɞɭ MNDO, |
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=AM1 |
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ɦɢɧɢɦɚɥɶɧɵɣ ɛɚɡɢɫ Ʌɟɜɞɢɧɚ ɞɥɹ ɪɚɫɱɟɬɚ ɩɨ ɦɟɬɨɞɭ AM1, |
=PM3 |
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ɦɢɧɢɦɚɥɶɧɵɣ ɛɚɡɢɫ Ʌɟɜɞɢɧɚ ɞɥɹ ɪɚɫɱɟɬɚ ɩɨ ɦɟɬɨɞɭ PM3. |
NGAUSS=2, 3, 4, 5, 6 ɟɫɥɢ GBASIS=STO, |
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=3, 6 |
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ɟɫɥɢ GBASIS= N21, |
=4, 5, 6 |
ɟɫɥɢ GBASIS= N31, |
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=6 |
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ɟɫɥɢ GBASIS= N311 – ɱɢɫɥɨ ɝɚɭɫɫɨɜɵɯ ɮɭɧɤɰɢɣ ɜ ɪɚɡɥɨɠɟɧɢɢ ȺɈ. |
NɊFUNC=1, 2, 3 ɱɢɫɥɨ ɩɨɥɹɪɢɡɚɰɢɨɧɧɵɯ ɪ-ɮɭɧɤɰɢɣ ɧɚ ɚɬɨɦɚɯ ɇ ɢɥɢ ɇɟ. ȿɫɥɢ ɜ ɦɨɥɟɤɭɥɟ ɷɬɢɯ ɚɬɨɦɨɜ ɧɟɬ, ɬɨ ɤɨɦɚɧɞɚ ɩɪɨɩɭɫɤɚɟɬɫɹ.
NDFUNC=1, 2, 3 ɱɢɫɥɨ ɩɨɥɹɪɢɡɚɰɢɨɧɧɵɯ d-ɮɭɧɤɰɢɣ ɧɚ ɬɹɠɟɥɵɯ ɚɬɨɦɚɯ (ɧɚɱɢɧɚɹ ɫ Na). ȿɫɥɢ ɜ ɦɨɥɟɤɭɥɟ ɷɬɢɯ ɚɬɨɦɨɜ ɧɟɬ, ɬɨ ɤɨɦɚɧɞɚ ɩɪɨɩɭɫɤɚɟɬɫɹ.
3 ɝɪɭɩɩɚ ɤɨɦɚɧɞ $DATA
ɫɨɫɬɨɢɬ ɢɡ ɪɹɞɚ ɫɬɪɨɤ, ɫɨɞɟɪɠɚɳɢɯ ɫɜɟɞɟɧɢɹ ɨ ɬɨɱɟɱɧɨɣ ɝɪɭɩɩɟ ɫɢɦɦɟɬɪɢɢ, ɤɨɨɪɞɢɧɚɬɚɯ ɚɬɨɦɨɜ – ɞɟɤɚɪɬɨɜɵɯ ɩɪɢ COORD=CART ɢɥɢ ɜɧɭɬɪɟɧɧɢɯ ɩɪɢ COORD=ZMT (ɫɦ. ɝɪɭɩɩɭ $CONTRL): ɋɬɪɨɤɚ 1. ɇɚɡɜɚɧɢɟ ɦɨɥɟɤɭɥɹɪɧɨɣ ɫɢɫɬɟɦɵ,
ɋɬɪɨɤɚ 2. Ɂɚɞɚɧɢɟ ɬɨɱɟɱɧɨɣ ɝɪɭɩɩɵ ɫɢɦɦɟɬɪɢɢ ɩɨ ɤɥɚɫɫɢɮɢɤɚɰɢɢ ɒɟɧɮɥɢɫɚ: C1, CS, CI, CN, S2N, CNH, CNV, DN, DNH, DND, T, TH, TD, O, OH. Ɉɩɪɟɞɟɥɢɬɶ ɫ ɩɨɦɨɳɶɸ ɩɪɟɩɨɞɚɜɚɬɟɥɹ. ɉɨɫɥɟ ɡɚɞɚɧɢɹ ɬɨɱɟɱɧɨɣ ɝɪɭɩɩɵ ɱɟɪɟɡ ɩɪɨɛɟɥ ɭɤɚɡɵɜɚɟɬɫɹ ɦɚɤɫɢɦɚɥɶɧɵɣ ɩɨɪɹɞɨɤ ɨɫɢ ɜɪɚɳɟɧɢɹ. ɇɚɩɪɢɦɟɪ, CNV 3 ɟɫɬɶ ɝɪɭɩɩɚ C3v.
ɋɬɪɨɤɚ 3. ɩɭɫɬɚɹ, ɟɫɥɢ ɜ ɫɪɨɤɟ 2 ɡɚɞɚɧɚ ɫɢɦɦɟɬɪɢɹ, ɨɬɥɢɱɧɚɹ ɨɬ ɋ1; ɟɫɥɢ ɋ1 ɬɨ ɫɬɪɨɤɚ ɨɩɭɫɤɚɟɬɫɹ.
ɋɬɪɨɤɢ ɫ 4 (ɢɥɢ 3, ɟɫɥɢ ɋ1) ɩɨ Ɇ (Ɇ- ɱɢɫɥɨ ɚɬɨɦɨɜ) - Z-ɦɚɬɪɢɰɚ ɜɧɭɬɪɟɧɧɢɯ ɤɨɨɪɞɢɧɚɬ ɩɪɢ
COORD=ZMT ɜ ɩɟɪɜɨɣ ɝɪɭɩɩɟ ɤɨɦɚɧɞ.
Ⱦɥɹ ɟɟ ɡɚɞɚɧɢɹ ɜɵɛɢɪɚɟɬɫɹ ɧɟɤɨɬɨɪɚɹ ɧɭɦɟɪɚɰɢɹ ɚɬɨɦɨɜ.
ɋɬɪɨɤɚ 4. Ⱦɥɹ ɚɬɨɦɚ N 1 ɡɚɞɚɟɬɫɹ ɯɢɦɢɱɟɫɤɢɣ ɫɢɦɜɨɥ (ɜ ɧɚɲɟɦ ɩɪɢɦɟɪɟ ɋl).
ɋɬɪɨɤɚ 5. Ⱦɥɹ ɚɬɨɦɚ N 2 (ɜ ɧɚɲɟɦ ɩɪɢɦɟɪɟ ɋ) ɡɚɩɢɫɶ 1– ɯɢɦɢɱɟɫɤɢɣ ɫɢɦɜɨɥ, ɡɚɩɢɫɶ 2 – N ɚɬɨɦɚ, ɫ ɤɨɬɨɪɵɦ ɨɧ ɫɜɹɡɚɧ ɫɨɝɥɚɫɧɨ ɜɵɛɪɚɧɧɨɣ ɧɭɦɟɪɚɰɢɢ (ɷɬɨɬ ɚɬɨɦ ɞɨɥɠɟɧ ɛɵɬɶ ɨɩɢɫɚɧ ɪɚɧɟɟ), ɡɚɩɢɫɶ 3 - ɞɥɢɧɚ ɫɜɹɡɢ ɦɟɠɞɭ ɪɚɫɫɦɚɬɪɢɜɚɟɦɨɣ ɩɚɪɨɣ ɚɬɨɦɨɜ (ɚɬɨɦ ɜ ɩɨɡɢɰɢɢ 2).
ɋɬɪɨɤɚ 6. Ⱦɥɹ ɚɬɨɦɚ N 3 (ɜ ɧɚɲɟɦ ɩɪɢɦɟɪɟ F): ɡɚɩɢɫɶ 1– ɯɢɦɢɱɟɫɤɢɣ ɫɢɦɜɨɥ; ɡɚɩɢɫɶ 2 – ɧɨɦɟɪ ɚɬɨɦɚ, ɫ ɤɨɬɨɪɵɦ ɨɧ ɫɜɹɡɚɧ (ɡɚɞɚɧɧɵɦ ɩɪɟɞɜɚɪɢɬɟɥɶɧɨ); ɡɚɩɢɫɶ 3 – ɞɥɢɧɚ ɫɜɹɡɢ ɫ ɚɬɨɦɨɦ ɜ ɩɨɡɢɰɢɢ 2; ɡɚɩɢɫɶ 4 – ɧɨɦɟɪ ɚɬɨɦɚ (ɡɚɞɚɧɧɨɝɨ ɩɪɟɞɜɚɪɢɬɟɥɶɧɨ), ɫ ɤɨɬɨɪɵɦ ɞɚɧɧɵɣ ɚɬɨɦ ɨɛɪɚɡɭɟɬ ɜɚɥɟɧɬɧɵɣ ɭɝɨɥ ɱɟɪɟɡ ɚɬɨɦ ɢɡ ɡɚɩɢɫɢ 2; ɡɚɩɢɫɶ 5 - ɱɢɫɥɟɧɧɨɟ ɡɧɚɱɟɧɢɟ ɷɬɨɝɨ ɜɚɥɟɧɬɧɨɝɨ ɭɝɥɚ.
ɋɬɪɨɤɢ 7 - M. Ɂɚɞɚɧɢɟ ɤɨɨɪɞɢɧɚɬ ɞɥɹ ɜɫɟɯ ɨɫɬɚɥɶɧɵɯ ɚɬɨɦɨɜ, ɧɚɱɢɧɚɹ ɫ ɚɬɨɦɚ ʋ 4, ɩɪɨɢɡɜɨɞɢɬɫɹ ɚɧɚɥɨɝɢɱɧɨ. ɋɨɞɟɪɠɚɧɢɟ ɡɚɩɢɫɟɣ 1 – 5 ɚɧɚɥɨɝɢɱɧɨ ɡɚɩɢɫɹɦ ɜ ɫɬɪɨɤɟ 6. Ɂɚɩɢɫɶ 6 - ɧɨɦɟɪ ɚɬɨɦɚ (ɷɬɨɬ ɚɬɨɦ ɞɨɥɠɟɧ ɛɵɬɶ ɨɩɢɫɚɧ ɪɚɧɟɟ) ɫ ɤɨɬɨɪɵɦ ɚɬɨɦɵ ɢɡ ɡɚɩɢɫɟɣ 2 ɢ 4 ɨɛɪɚɡɭɸɬ ɩɥɨɫɤɨɫɬɶ, ɚ ɞɚɧɧɵɣ ɚɬɨɦ ɨɛɪɚɡɭɟɬ ɫ ɷɬɨɣ ɩɥɨɫɤɨɫɬɶɸ ɞɜɭɝɪɚɧɧɵɣ ɭɝɨɥ, ɡɚɩɢɫɶ 7 - ɱɢɫɥɟɧɧɨɟ ɡɧɚɱɟɧɢɟ ɷɬɨɝɨ ɞɜɭɝɪɚɧɧɨɝɨ ɭɝɥɚ.
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
3 |
ȿɫɥɢ ɱɢɫɥɟɧɧɵɟ ɡɧɚɱɟɧɢɹ ɜɫɟɯ ɞɥɢɧ ɫɜɹɡɟɣ (Å), ɜɚɥɟɧɬɧɵɯ ɢ ɞɜɭɝɪɚɧɧɵɯ ɭɝɥɨɜ (ɝɪɚɞ.) ɡɚɞɚɸɬɫɹ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ, ɤɨɦɚɧɞɧɚɹ ɝɪɭɩɩɚ $DATA ɡɚɤɚɧɱɢɜɚɟɬɫɹ.
ȿɫɥɢ ɬɟ ɤɨɨɪɞɢɧɚɬɵ, ɤɨɬɨɪɵɟ ɩɪɢ ɨɩɬɢɦɢɡɚɰɢɢ ɝɟɨɦɟɬɪɢɢ ɞɨɥɠɧɵ ɨɫɬɚɜɚɬɶɫɹ ɪɚɜɧɵɦɢ ɞɪɭɝ ɞɪɭɝɭ, ɡɚɞɚɸɬɫɹ ɛɭɤɜɟɧɧɵɦɢ ɜɵɪɚɠɟɧɢɹɦɢ, ɤɨɦɚɧɞɧɚɹ ɝɪɭɩɩɚ $DATA ɩɪɨɞɨɥɠɚɟɬɫɹ ɫɥɟɞɭɸɳɢɦɢ ɫɬɪɨɤɚɦɢ:
1)ɉɭɫɬɚɹ ɫɬɪɨɤɚ;
2)Ɂɚɞɚɧɢɟ ɱɢɫɥɟɧɧɵɯ ɡɧɚɱɟɧɢɣ ɪɚɫɫɬɨɹɧɢɣ ɢ ɭɝɥɨɜ, ɨɩɪɟɞɟɥɟɧɧɵɯ ɛɭɤɜɟɧɧɵɦɢ ɜɵɪɚɠɟɧɢɹɦɢ.
ɋɨɜɟɬ: ɟɫɥɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɞɚɧɧɵɟ ɨ ɝɟɨɦɟɬɪɢɢ ɦɨɥɟɤɭɥɵ ɨɬɫɭɬɫɬɜɭɸɬ, ɧɚɱɚɥɶɧɨɟ ɩɪɢɛɥɢɠɟɧɢɟ ɫɥɟɞɭɟɬ ɢɫɤɚɬɶ ɪɚɫɱɟɬɨɦ ɜ ɦɢɧɢɦɚɥɶɧɨɦ ɛɚɡɢɫɟ, ɩɨɫɬɟɩɟɧɧɨ ɟɝɨ ɪɚɫɲɢɪɹɹ.
ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɞɥɢɧ ɢ ɷɧɟɪɝɢɣ ɧɟɤɨɬɨɪɵɯ ɫɜɹɡɟɣ
|
|
ɗɧɟɪɝɢɢ |
Ⱦɥɢɧɵ ɫɜɹɡɟɣ |
Ⱦɜɭɯɚɬɨɦɧɵɟ |
ɋɜɹɡɢ ɜ ɦɧɨɝɨɚɬɨɦɧɵɯ |
(Å)ɦɨɥɟɤɭɥɵ(ɤɤɚɥ/ɦɨɥɶ) ɦɨɥɟɤɭɥɚɯ(ɤɤɚɥ/ɦɨɥɶ)
H-C |
1.09 |
H-H |
104 |
H-C |
99 |
H-N |
1.00 |
O=O |
119 |
H-N |
93 |
H-O |
0.96 |
N=N |
226 |
H-O |
111 |
C-C |
1.54 |
H-F |
135 |
C-C |
83 |
C-N |
1.47 |
H-Cl |
103 |
C-N |
73 |
C-O |
1.43 |
H-Br |
88 |
C-O |
86 |
C-Cl |
1.76 |
H-I |
71 |
C-Cl |
81 |
P-O |
1.57 |
F-F |
37 |
C-F |
116 |
C=C |
1.35 |
Cl-Cl |
58 |
C=C |
146 |
C=N |
1.30 |
Br-Br |
46 |
C=N |
147 |
C=O |
1.22 |
I-I |
36 |
C=O |
179 |
P=O |
1.47 |
|
|
C{C |
200 |
Ȼɨɥɟɟ ɩɨɥɧɵɟ ɞɚɧɧɵɟ ɫɦ. ɜ ɪɚɛɨɬɟ: F.H. Allen, et al. Journal of the Chemical Society Perkins Transactions II (1987): S1-S19.
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Ɉɬɱɟɬ ɩɨ ɪɚɛɨɬɟ ɞɨɥɠɟɧ ɫɨɫɬɨɹɬɶ ɢɡ ɬɪɟɯ ɱɚɫɬɟɣ, ɫɨɞɟɪɠɚɳɢɯ ɫɥɟɞɭɸɳɢɣ ɦɚɬɟɪɢɚɥ:
1.Ɏɨɪɦɭɥɢɪɨɜɤɚ ɰɟɥɢ ɢ ɡɚɞɚɱ ɤɜɚɧɬɨɜɨ-ɯɢɦɢɱɟɫɤɢɯ ɪɚɫɱɟɬɨɜ. Ɂɚɞɚɱɚ ɞɚɧɧɨɝɨ ɪɚɫɱɟɬɚ ɜ ɪɚɦɤɚɯ ɨɛɳɟɣ ɡɚɞɚɱɢ.
2.ɏɚɪɚɤɬɟɪɢɫɬɢɤɚ ɧɟɷɦɩɢɪɢɱɟɫɤɢɯ ɪɚɫɱɟɬɨɜ. Ɉɛɨɫɧɨɜɚɧɢɟ ɜɵɛɨɪɚ ɦɟɬɨɞɚ ɪɚɫɱɟɬɚ ɢ ɛɚɡɢɫɚ ɞɥɹ ɪɟɲɟɧɢɹ ɩɨɫɬɚɜɥɟɧɧɨɣ ɡɚɞɚɱɢ. Ɉɩɢɫɚɧɢɟ ɫɩɨɫɨɛɚ ɩɨɫɬɪɨɟɧɢɹ ɛɚɡɢɫɧɨɝɨ ɧɚɛɨɪɚ.
3.ɂɧɬɟɪɩɪɟɬɚɰɢɹ ɪɟɡɭɥɶɬɚɬɨɜ ɪɚɫɱɟɬɚ.
ɂɇɌȿɊɉɊȿɌȺɐɂə ɊȿɁɍɅɖɌȺɌɈȼ ɊȺɋɑȿɌȺ ɩɪɨɜɨɞɢɬɫɹ ɩɨ ɫɥɟɞɭɸɳɢɦ ɩɨɡɢɰɢɹɦ.
1. Ɉɰɟɧɤɚ ɫɬɚɛɢɥɶɧɨɫɬɢ ɦɨɥɟɤɭɥɵ.
ɗɧɟɪɝɢɹ ɨɛɪɚɡɨɜɚɧɢɹ ɦɨɥɟɤɭɥɵ Ⱥȼɋ3 ɢɡ ɩɪɨɫɬɵɯ ɜɟɳɟɫɬɜ (ɢɧɚɱɟ - ɷɧɬɚɥɶɩɢɹ ɨɛɪɚɡɨɜɚɧɢɹ ɦɨ-
ɥɟɤɭɥɵ Ⱥȼɋ3 ɩɪɢ 0Ʉ ɜ ɛɟɫɤɨɧɟɱɧɨ ɪɚɡɪɟɠɟɧɧɨɦ ɝɚɡɟ ɛɟɡ ɭɱɟɬɚ ɷɧɟɪɝɢɢ ɧɭɥɟɜɵɯ ɤɨɥɟɛɚɧɢɣ) ɨɩɪɟ-
ɞɟɥɹɟɬɫɹ ɤɚɤ
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
4 |
'fH0 (Ⱥȼɋ3) = E(Ⱥȼɋ3) – 1/2E(Ⱥ2) – 1/2E(ȼ2) – 3/2E(ɋ2) |
|
E(Ⱥȼɋ3) – ɩɨɥɧɚɹ ɷɧɟɪɝɢɹ ɦɨɥɟɤɭɥɵ, ɩɨɥɭɱɟɧɧɚɹ ɜ ɞɚɧɧɨɣ ɪɚɛɨɬɟ.
ȼɧɢɦɚɧɢɟ! ɉɨɥɧɚɹ ɷɧɟɪɝɢɹ ɦɨɥɟɤɭɥɵ ɜ ɜɵɞɚɱɟ ɩɪɨɝɪɚɦɦɧɨɝɨ ɤɨɦɩɥɟɤɫɚ GAMESS ɜɵɪɚɠɚɟɬɫɹ ɜ ɚɬɨɦɧɵɯ ɟɞɢɧɢɰɚɯ ɷɧɟɪɝɢɢ (ɟɞɢɧɢɰɚɯ ɏɚɪɬɪɢ): 1 ɚ.ɟ. = 627.51 ɤɤɚɥ/ɦɨɥɶ = 2625.5 ɤȾɠ/ɦɨɥɶ = 27, 212 ɷȼ.
ɋɪɚɜɧɢɬɶ 'fH0 (Ⱥȼɋ3) ɫ ɷɤɫɩɟɪɢɦɟɧɬɨɦ. ɉɪɢ ɨɬɫɭɬɫɬɜɢɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ ɫɪɚɜɧɢɬɶ ɫ 'fH0 ɩɨɞɨɛɧɵɯ ɫɨɟɞɢɧɟɧɢɣ, ɢ ɧɚ ɨɫɧɨɜɚɧɢɢ ɜɟɥɢɱɢɧɵ ɢ ɡɧɚɤɚ ɷɧɟɪɝɢɢ ɫɞɟɥɚɬɶ ɜɵɜɨɞ ɨ ɫɬɚɛɢɥɶ-
ɧɨɫɬɢ.
2. ɋɜɨɣɫɬɜɚ ɫɜɹɡɟɣ ɦɨɥɟɤɭɥɵ.
¾ɋɪɚɜɧɢɬɶ ɝɟɨɦɟɬɪɢɸ ɦɨɥɟɤɭɥɵ (ɦɟɠɴɹɞɟɪɧɵɟ ɪɚɫɫɬɨɹɧɢɹ ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ) ɫ ɷɤɫɩɟɪɢɦɟɧɬɨɦ.
ɉɪɢ ɨɬɫɭɬɫɬɜɢɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ ɫɪɚɜɧɢɬɶ ɫ ɝɟɨɦɟɬɪɢɟɣ ɩɨɞɨɛɧɵɯ ɫɨɟɞɢɧɟɧɢɣ, ɢ
ɧɚ ɨɫɧɨɜɚɧɢɢ ɨɛɳɧɨɫɬɢ ɛɚɡɢɫɚ ɨɰɟɧɢɬɶ ɬɨɱɧɨɫɬɶ ɪɚɫɱɟɬɚ.
¾ɋɨɩɨɫɬɚɜɥɹɹ ɞɥɢɧɵ ɫɜɹɡɟɣ, ɩɨɪɹɞɤɢ ɫɜɹɡɟɣ ɢ ɜɚɥɟɧɬɧɨɫɬɢ ɚɬɨɦɨɜ ɩɨ Ʉɨɭɥɫɨɧɭ ɫ ɬɚɤɨɜɵɦɢ ɜ ɫɭɝɭɛɨ ɤɨɜɚɥɟɧɬɧɵɯ ɢ ɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɹɯ, ɤɚɱɟɫɬɜɟɧɧɨ ɨɰɟɧɢɬɶ ɫɬɟɩɟɧɶ ɤɨɜɚɥɟɧɬɧɨ-
ɫɬɢ/ɢɨɧɧɨɫɬɢ ɫɜɹɡɟɣ ɜ ɢɫɫɥɟɞɭɟɦɨɣ ɦɨɥɟɤɭɥɟ.
3.ɉɨɫɬɪɨɟɧɢɟ ɞɢɚɝɪɚɦɦɵ ɷɧɟɪɝɟɬɢɱɟɫɤɢɯ ɭɪɨɜɧɟɣ.
4.Ɉɩɪɟɞɟɥɟɧɢɟ ɧɭɤɥɟɨɮɢɥɶɧɵɯ / ɷɥɟɤɬɪɨɮɢɥɶɧɵɯ ɫɜɨɣɫɬɜ ɦɨɥɟɤɭɥɵ:
Ɉɫɭɳɟɫɬɜɥɹɟɬɫɹ ɩɨ ɡɧɚɤɭ ɷɧɟɪɝɢɢ ɇȼɆɈ (ɧɢɠɧɟɣ ɜɚɤɚɧɬɧɨɣ ɆɈ) ɦɨɥɟɤɭɥɵ:
¾ ɡɧɚɤ «+» – ɧɭɤɥɟɨɮɢɥ; ɡɧɚɤ «-» - ɷɥɟɤɬɪɨɮɢɥ (ɨɛɴɹɫɧɢɬɶ ɩɨɱɟɦɭ).
Ɉɩɪɟɞɟɥɟɧɢɟ ɠɟɫɬɤɨɫɬɢ ɢ ɦɹɝɤɨɫɬɢ ɦɨɥɟɤɭɥɵ. Ɋɟɚɝɟɧɬ ɫɱɢɬɚɟɬɫɹ ɠɟɫɬɤɢɦ, ɟɫɥɢ ɷɧɟɪɝɟɬɢ-
ɱɟɫɤɚɹ ɳɟɥɶ ɦɟɠɞɭ ȼɁɆɈ ɢ ɇȼɆɈ ɩɪɟɜɵɲɚɟɬ 1 ɷȼ; ɪɟɚɝɟɧɬ ɫɱɢɬɚɟɬɫɹ ɦɹɝɤɢɦ, ɟɫɥɢ ɷɧɟɪɝɟɬɢɱɟ-
ɫɤɚɹ ɳɟɥɶ ɦɟɠɞɭ ȼɁɆɈ ɢ ɇȼɆɈ ɦɟɧɟɟ 1 ɷȼ;
ɀɟɫɬɤɨɫɬɶ ɦɨɥɟɤɭɥɵ ɪɚɫɫɱɢɬɵɜɚɟɬɫɹ ɩɨ ɮɨɪɦɭɥɟ: |
K = |
1 |
|
(ȿɇȼɆɈ – ȿȼɁɆɈ). |
|
||||
2 |
|
|
|||||||
|
|
|
|
|
|
|
|
||
Ɇɹɝɤɨɫɬɶ ɦɨɥɟɤɭɥɵ ɫɜɹɡɚɧɚ ɫ ɠɟɫɬɤɨɫɬɶɸ ɫɨɨɬɧɨɲɟɧɢɟɦ: |
S= |
1 |
|
, |
S= |
|
1 |
. |
|
|
|
(ȿɇȼɆɈ |
ȿȼɁɆɈ ) |
||||||
|
|
2Ș |
|
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|||||
5. Ɉɩɪɟɞɟɥɟɧɢɟ ɩɨɥɨɠɟɧɢɹ ɪɟɚɤɰɢɨɧɧɵɯ ɰɟɧɬɪɨɜ.
¾ɉɨɥɨɠɟɧɢɟ ɪɟɚɤɰɢɨɧɧɵɯ ɰɟɧɬɪɨɜ ɜ ɠɟɫɬɤɢɯ ɪɟɚɝɟɧɬɚɯ ɩɪɢɛɥɢɠɟɧɧɨ ɨɩɪɟɞɟɥɹɟɬɫɹ ɡɚɪɹɞɚɦɢ ɧɚ ɚɬɨɦɚɯ. ɉɪɢɜɟɫɬɢ ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɡɚɪɹɞɨɜ ɧɚ ɚɬɨɦɚɯ ɢɫɫɥɟɞɭɟɦɨɣ ɦɨɥɟɤɭɥɵ ɩɨ Ɇɚɥɥɢɤɟɧɭ ɢ ɧɚ ɨɫɧɨɜɚɧɢɢ ɢɯ ɜɟɥɢɱɢɧ ɢ ɡɧɚɤɨɜ ɫɞɟɥɚɬɶ ɜɵɜɨɞ ɨ ɧɚɢɛɨɥɟɟ ɜɟɪɨɹɬɧɵɯ ɧɚɩɪɚɜɥɟɧɢɹɯ ɚɬɚɤ.
¾ɉɨɥɨɠɟɧɢɟ ɪɟɚɤɰɢɨɧɧɵɯ ɰɟɧɬɪɨɜ ɜ ɦɹɝɤɢɯ ɪɟɚɝɟɧɬɚɯ ɨɩɪɟɞɟɥɹɟɬɫɹ ɝɪɚɧɢɱɧɨɣ ɩɥɨɬɧɨɫɬɶɸ ɷɥɟɤɬɪɨɧɨɜ ɧɚ ɚɬɨɦɚɯ. Ƚɪɚɧɢɱɧɚɹ ɩɥɨɬɧɨɫɬɶ ɷɥɟɤɬɪɨɧɨɜ ɧɚ ɚɬɨɦɟ Ⱥ ɪɚɫɫɱɢɬɵɜɚɟɬɫɹ ɩɨ ɮɨɪɦɭ-
ɥɟ: fA 2¦ciµ2 , ɝɞɟ ciP - ɤɨɷɮɮɢɰɢɟɧɬɵ ɪɚɡɥɨɠɟɧɢɹ ɝɪɚɧɢɱɧɨɣ ɆɈ (ȼɁɆɈ ɧɭɤɥɟɨɮɢɥɚ ɢɥɢ
µ A
ɇȼɆɈ ɷɥɟɤɬɪɨɮɢɥɚ) ɩɨ ȺɈ, ɰɟɧɬɪɢɪɨɜɚɧɧɵɦ ɧɚ ɚɬɨɦɟ Ⱥ. Ɋɚɫɫɱɢɬɚɬɶ ɜɟɥɢɱɢɧɵ fȺ ɢ ɧɚ ɢɯ ɨɫ-
ɧɨɜɚɧɢɢ ɫɞɟɥɚɬɶ ɜɵɜɨɞ ɨ ɧɚɢɛɨɥɟɟ ɜɟɪɨɹɬɧɵɯ ɧɚɩɪɚɜɥɟɧɢɹɯ ɚɬɚɤ.
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
5 |
6.Ɉɰɟɧɤɚ ɪɚɫɬɜɨɪɢɦɨɫɬɢ.
ɉɪɨɢɡɜɨɞɢɬɫɹ ɫɪɚɜɧɟɧɢɟɦ ɷɥɟɤɬɪɢɱɟɫɤɨɝɨ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɚ ɦɨɥɟɤɭɥɵ ɫ ɞɢɩɨɥɶɧɵɦɢ ɦɨ-
ɦɟɧɬɚɦɢ ɢɡɜɟɫɬɧɵɯ ɪɚɫɬɜɨɪɢɬɟɥɟɣ, ɧɚɩɪɢɦɟɪ:
P(ɇ2Ɉ) = 1.83 D, P(Cɇ3ɈH) = 1.69 D (ɩɨɥɹɪɧɵɟ ɪɚɫɬɜɨɪɢɬɟɥɢ).
ɇɚ ɨɫɧɨɜɚɧɢɢ ɛɥɢɡɨɫɬɢ ɞɢɩɨɥɶɧɵɯ ɦɨɦɟɧɬɨɜ ɞɟɥɚɟɬɫɹ ɜɵɜɨɞ ɨ ɩɪɟɢɦɭɳɟɫɬɜɟɧɧɨɣ ɪɚɫɬɜɨ-
ɪɢɦɨɫɬɢ ɜ ɩɨɥɹɪɧɨɦ ɢɥɢ ɜ ɧɟɩɨɥɹɪɧɨɦ ɪɚɫɬɜɨɪɢɬɟɥɟ.
ɉɊɂɆȿɊ ɈɌɑȿɌȺ
ɇɟɷɦɩɢɪɢɱɟɫɤɢɣ ɤɜɚɧɬɨɜɨ-ɯɢɦɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɦɨɥɟɤɭɥɵ CClF3.
1. ɐȿɅɂ ɂ ɁȺȾȺɑɂ ɊȺɋɑȿɌȺ.
ɐɟɥɶ ɪɚɫɱɟɬɚ: Ɉɩɪɟɞɟɥɟɧɢɟ ɤɪɢɬɟɪɢɟɜ ɜɵɛɨɪɚ ɢ ɢɡɭɱɟɧɢɟ ɩɪɢɧɰɢɩɨɜ ɩɨɫɬɪɨɟɧɢɹ ɫɬɚɧ-
ɞɚɪɬɧɨɝɨ ɛɚɡɢɫɧɨɝɨ ɧɚɛɨɪɚ ɞɥɹ ɪɚɫɱɟɬɚ ɦɨɥɟɤɭɥɹɪɧɵɯ ɫɢɫɬɟɦ. ɂɡɭɱɟɧɢɟ ɦɟɬɨɞɨɜ ɢɧɬɟɪɩɪɟɬɚɰɢɢ ɪɟɡɭɥɶɬɚɬɨɜ ɪɚɫɱɟɬɚ ɢ ɩɪɟɞɫɬɚɜɥɟɧɢɹ ɦɨɥɟɤɭɥɵ ɜ ɜɢɞɟ ɜɟɤɬɨɪɚ ɫɜɨɣɫɬɜ ɧɚ ɢɯ ɨɫɧɨɜɟ. Ɂɧɚɤɨɦɫɬɜɨ ɫ ɩɪɨɝɪɚɦɦɧɵɦ ɤɨɦɩɥɟɤɫɨɦ GAMESS.
Ɂɚɞɚɱɚ ɪɚɫɱɟɬɚ: ȼɵɛɪɚɬɶ ɧɚɢɦɟɧɶɲɢɣ ɢɡ ɜɨɡɦɨɠɧɵɯ ɨɩɬɢɦɚɥɶɧɵɣ ɛɚɡɢɫ ɞɥɹ ɧɟɷɦɩɢɪɢɱɟ-
ɫɤɨɝɨ ɪɚɫɱɟɬɚ ɞɥɢɧ ɫɜɹɡɟɣ ɢ ɜɚɥɟɧɬɧɵɯ ɭɝɥɨɜ ɦɨɥɟɤɭɥɵ CClF3 ɫ ɩɨ ɩɪɨɝɪɚɦɦɧɨɦɭ ɤɨɦɩɥɟɤɫɭ
GAMESS ɫ ɬɨɱɧɨɫɬɶɸ ɩɨɪɹɞɤɚ 0.01 Å ɞɥɹ ɞɥɢɧ ɫɜɹɡɟɣ ɢ 1 ɝɪɚɞɭɫ ɞɥɹ ɜɚɥɟɧɬɧɵɯ ɭɝɥɨɜ, ɫɪɚɜɧɢɦɨɣ ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɣ. ɇɚ ɨɫɧɨɜɚɧɢɢ ɪɟɡɭɥɶɬɚɬɨɜ ɪɚɫɱɟɬɚ ɨɰɟɧɢɬɶ ɫɬɚɛɢɥɶɧɨɫɬɶ ɢ ɮɚɤɬɨɪɵ, ɨɩɪɟ-
ɞɟɥɹɸɳɢɟ ɪɟɚɤɰɢɨɧɧɭɸ ɫɩɨɫɨɛɧɨɫɬɶ ɷɬɨɣ ɦɨɥɟɤɭɥɵ.
2. ɏȺɊȺɄɌȿɊɂɋɌɂɄȺ ɂ ɈȻɈɋɇɈȼȺɇɂȿ ɆȿɌɈȾȺ ɊȺɋɑȿɌȺ
Ɋɚɫɱɟɬ ɦɨɥɟɤɭɥɵ CClF3 ɨɫɭɳɟɫɬɜɥɟɧ ɩɨ ɩɪɨɝɪɚɦɦɧɨɦɭ ɤɨɦɩɥɟɤɫɭ GAMESS ɜ ɫɬɚɧɞɚɪɬɧɨɦ ɛɚɡɢɫɧɨɦ (ɜɚɥɟɧɬɧɨ-ɪɚɫɳɟɩɥɟɧɧɨɦ) ɧɚɛɨɪɟ ɉɨɩɥɚ 6-31G*. ȼɚɥɟɧɬɧɵɟ ȺɈ ɩɪɟɞɫɬɚɜɥɟɧɵ ɥɢɧɟɣɧɵ-
ɦɢ ɤɨɦɛɢɧɚɰɢɹɦɢ 2 ɫɠɚɬɵɯ ɤɨɦɛɢɧɚɰɢɣ ɝɚɭɫɫɨɜɵɯ ɨɪɛɢɬɚɥɟɣ, ɨɫɬɨɜɧɵɟ ȺɈ – 1-ɣ. ɇɚ ɤɚɠɞɨɦ ɧɟ-
ɜɨɞɨɪɨɞɧɨɦ ɚɬɨɦɟ ɬɚɤɠɟ ɰɟɧɬɪɢɪɨɜɚɧɨ ɩɨ 6 ɤɨɦɩɨɧɟɧɬ ɩɨɥɹɪɢɡɚɰɢɨɧɧɵɯ d-ɮɭɧɤɰɢɣ. Ɍɚɤɢɦ ɨɛɪɚ-
ɡɨɦ, ɛɚɡɢɫ ɞɥɹ ɪɚɫɱɟɬɚ ɦɨɥɟɤɭɥɵ CClF3 ɫɨɫɬɨɢɬ ɢɡ 79 ɮɭɧɤɰɢɣ:
1*C(1(1s) + 2*4(2s + 2p) + 6(3d)) +
1*Cl (1(1s) + 4(2s + 2p) + 2*4(3s + 3p) + 6(3d)) + 3*F(1(1s) + 4*2(2s + 2p) + 6(3d)) = 79.
ȼɫɟ ɜɚɥɟɧɬɧɵɟ ɛɚɡɢɫɧɵɟ ɮɭɧɤɰɢɢ ɞɜɭɯɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɟ (6-31G*), ɨɫɬɨɜɧɵɟ 1s ȺɈ - ɨɞɧɨ-
ɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɟ. s- ɢ p-ɫɠɚɬɵɟ ɝɚɭɫɫɨɜɵ ɨɪɛɢɬɚɥɢ, ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɟ (ɫ ɮɨɪɦɚɥɶɧɨɣ ɬɨɱɤɢ ɡɪɟ-
ɧɢɹ) ɝɥɚɜɧɨɦɭ ɤɜɚɧɬɨɜɨɦɭ ɱɢɫɥɭ, ɫɜɟɪɧɭɬɵ ɜ sp-ɨɛɨɥɨɱɤɢ [(2s + 2p), (3s + 3p)] ɢ ɩɪɟɞɫɬɚɜɥɟɧɵ ɪɚɡ-
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
6 |
ɥɢɱɧɵɦɢ ɥɢɧɟɣɧɵɦɢ ɤɨɦɛɢɧɚɰɢɹɦɢ ɝɚɭɫɫɨɜɵɯ ɩɪɢɦɢɬɢɜɨɜ ɫ ɨɞɢɧɚɤɨɜɵɦɢ ɷɤɫɩɨɧɟɧɰɢɚɥɶɧɵɦɢ ɦɧɨɠɢɬɟɥɹɦɢ.
Ʉɚɠɞɚɹ ɨɫɬɨɜɧɚɹ ɨɪɛɢɬɚɥɶ ɩɪɟɞɫɬɚɜɥɟɧɚ ɥɢɧɟɣɧɨɣ ɤɨɦɛɢɧɚɰɢɟɣ ɢɡ 6 ɝɚɭɫɫɨɜɵɯ ɩɪɢɦɢɬɢ-
ɜɨɜ (6-31G*). Ʉɚɠɞɚɹ ɨɪɛɢɬɚɥɶ ɞɥɹ ɜɚɥɟɧɬɧɵɯ ɷɥɟɤɬɪɨɧɨɜ ɩɪɟɞɫɬɚɜɥɟɧɚ ɥɢɧɟɣɧɨɣ ɤɨɦɛɢɧɚɰɢɟɣ ɥɢɛɨ ɢɡ 3 (6-31G*), ɥɢɛɨ ɢɡ 1 (6-31G*) ɝɚɭɫɫɨɜɵɯ ɩɪɢɦɢɬɢɜɨɜ.
Ȼɚɡɢɫ 6-31G* ɹɜɥɹɟɬɫɹ ɧɚɢɦɟɧɶɲɢɦ ɢɡ ɜɨɡɦɨɠɧɵɯ ɛɚɡɢɫɨɜ, ɩɪɢɝɨɞɧɵɦ ɞɥɹ ɪɚɫɱɟɬɚ ɞɥɢɧ ɫɜɹɡɟɣ ɢ ɜɚɥɟɧɬɧɵɯ ɭɝɥɨɜ ɦɨɥɟɤɭɥɵ CClF3 ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɣ ɬɨɱɧɨɫɬɶɸ. Ⱦɨɛɚɜɥɟɧɢɟ ɩɨɥɹɪɢɡɚ-
ɰɢɨɧɧɵɯ d-ɮɭɧɤɰɢɣ (6-31G*) ɭɱɢɬɵɜɚɟɬ ɩɨɥɹɪɢɡɚɰɢɸ ɷɥɟɤɬɪɨɧɧɵɯ ɨɛɨɥɨɱɟɤ ɚɬɨɦɨɜ ɝɚɥɨɝɟɧɨɜ ɩɪɢ ɨɛɪɚɡɨɜɚɧɢɢ ɫɜɹɡɟɣ; ɷɬɨ ɨɛɟɫɩɟɱɢɜɚɟɬ ɭɦɟɧɶɲɟɧɢɟ ɞɥɢɧɵ ɫɜɹɡɟɣ ɧɚ ~ 0.05 Å.
3. ɂɇɌȿɊɉɊȿɌȺɐɂə ɊȿɁɍɅɖɌȺɌɈȼ ɊȺɋɑȿɌȺ
1. Ɉɰɟɧɤɚ ɫɬɚɛɢɥɶɧɨɫɬɢ ɦɨɥɟɤɭɥɵ.
ɗɧɬɚɥɶɩɢɹ ɨɛɪɚɡɨɜɚɧɢɹ ɦɨɥɟɤɭɥɵ CClF3 ɢɡ ɩɪɨɫɬɵɯ ɜɟɳɟɫɬɜ ɪɚɜɧɚ:
'fH0 (CClF3) = E(CClF3) – 1/2E(C2) – 1/2E(Cl2)– 3/2E(F2) = -795.6632 + ½*918.91282 + 3/2*198.67776 + ½*75.37903 = -0.50065 ɚ.ɟ. = -314.16 ɤɤɚɥ/ɦɨɥɶ = -1314.5 ɤȾɠ/ɦɨɥɶ
ȼɵɜɨɞ: Ɇɨɥɟɤɭɥɚ CClF3 ɫɬɚɛɢɥɶɧɚ ɩɪɢ ɫɬɚɧɞɚɪɬɧɵɯ ɭɫɥɨɜɢɹɯ.
2. ɋɜɨɣɫɬɜɚ ɫɜɹɡɟɣ ɦɨɥɟɤɭɥɵ CClF3.
ɍɬɨɱɧɟɧɧɚɹ ɝɟɨɦɟɬɪɢɹ ɢ ɩɨɪɹɞɤɢ ɫɜɹɡɟɣ ɦɨɥɟɤɭɥɵ CClF3:
ɋɜɹɡɶ |
Å |
ɩɨɪɹɞɨɤ ɫɜɹɡɢ |
ȼɚɥɟɧɬɧɵɣ ɭɝɨɥ |
ɝɪɚɞ |
C-CL |
1.747 |
1.089 |
|
|
ɋ-F |
1.306 |
0.959 |
CL/ɋ\F |
110.26 |
|
|
|
|
|
ɇɟɷɦɩɢɪɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɜ ɛɚɡɢɫɟ 6-31G* ɩɨɡɜɨɥɹɟɬ ɩɨɥɭɱɢɬɶ ɝɟɨɦɟɬɪɢɸ ɦɨɥɟɤɭɥɵ CClF3 ɢ
ɩɨɞɨɛɧɵɯ ɟɣ ɦɨɥɟɤɭɥ (ɋCl4, CɇF3, ɋɇCl3), ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɣ ɬɨɱɧɨɫɬɶɸ.
ȼɚɥɟɧɬɧɨɫɬɶ ɚɬɨɦɨɜ ɩɨ Ʉɨɭɥɫɨɧɭ ɜ ɦɨɥɟɤɭɥɟ CClF3:
|
ATOM |
ȼȺɅȿɇɌɇɈɋɌɖ |
1 |
CL |
1.104 |
2 |
C |
3.967 |
3 |
F |
0.973 |
ɋɨɩɨɫɬɚɜɥɹɹ ɞɥɢɧɭ ɫɜɹɡɟɣ ɜ ɦɨɥɟɤɭɥɟ CClF3 ɫ ɢɯ ɩɨɪɹɞɤɨɦ ɢ ɜɚɥɟɧɬɧɨɫɬɶɸ ɚɬɨɦɨɜ, ɦɨɠɧɨ ɫɞɟ-
ɥɚɬɶ ɜɵɜɨɞ: ɋɜɹɡɢ ɜ ɦɨɥɟɤɭɥɟ CClF3 ɤɨɜɚɥɟɧɬɧɵɟ. 3. ɗɧɟɪɝɟɬɢɱɟɫɤɚɹ ɞɢɚɝɪɚɦɦɚ (ɚ.ɟ.): (ɩɪɢɜɟɫɬɢ!)
4.Ɉɩɪɟɞɟɥɟɧɢɟ ɧɭɤɥɟɨɮɢɥɶɧɵɯ ɢ ɷɥɟɤɬɪɨɮɢɥɶɧɵɯ ɫɜɨɣɫɬɜ ɦɨɥɟɤɭɥɵ CClF3.
ɗɧɟɪɝɢɹ ɇȼɆɈ ɦɨɥɟɤɭɥɵ CClF3 ɩɨɥɨɠɢɬɟɥɶɧɚ (0.1798 ɚ.ɟ.).
ȼɵɜɨɞ: Ɇɨɥɟɤɭɥɚ CClF3 ɧɭɤɥɟɨɮɢɥ.
Ʉɚɮɟɞɪɚ ɤɜɚɧɬɨɜɨɣ ɯɢɦɢɢ ɊɏɌɍ ɢɦ. Ⱦ.ɂ. Ɇɟɧɞɟɥɟɟɜɚ, 2004 ɝ. |
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5. Ɉɩɪɟɞɟɥɟɧɢɟ ɠɟɫɬɤɨɫɬɢ ɢ ɦɹɝɤɨɫɬɢ ɦɨɥɟɤɭɥɵ.
ɀɟɫɬɤɨɫɬɶ ɦɨɥɟɤɭɥɵ CClF3:
K = 12 (ȿɇȼɆɈ – ȿȼɁɆɈ) = ½(0.1798 + 0.5011) = 0.3404 ɚ.ɟ = 9.25 ɷȼ.
ȼɵɜɨɞ: Ɇɨɥɟɤɭɥɚ CClF3 ɹɜɥɹɟɬɫɹ ɠɟɫɬɤɢɦ ɪɟɚɝɟɧɬɨɦ.
6. Ɉɩɪɟɞɟɥɟɧɢɟ ɩɨɥɨɠɟɧɢɹ ɪɟɚɤɰɢɨɧɧɵɯ ɰɟɧɬɪɨɜ.
Ɋɟɚɤɰɢɨɧɧɚɹ ɫɩɨɫɨɛɧɨɫɬɶ ɦɨɥɟɤɭɥɵ CClF3 ɤɚɤ ɠɟɫɬɤɨɝɨ ɪɟɚɝɟɧɬɚ ɨɩɪɟɞɟɥɹɟɬɫɹ ɡɚɪɹɞɚɦɢ ɧɚ ɚɬɨ-
ɦɚɯ. Ɋɚɫɩɪɟɞɟɥɟɧɢɟ ɡɚɪɹɞɨɜ ɧɚ ɚɬɨɦɚɯ ɩɨ Ɇɚɥɥɢɤɟɧɭ ɫɥɟɞɭɸɳɟɟ:
ATOM |
ɁȺɊəȾ |
|
1 CL |
0.004 |
|
2 |
C |
0.922 |
3 |
F |
-0.308 |
Ɇɚɤɫɢɦɚɥɶɧɵɣ ɨɬɪɢɰɚɬɟɥɶɧɵɣ ɡɚɪɹɞ ɤɨɧɰɟɧɬɪɢɪɭɟɬɫɹ ɧɚ ɚɬɨɦɚɯ F.
ȼɵɜɨɞ: Ⱥɬɨɦɵ F – ɧɚɢɛɨɥɟɟ ɜɟɪɨɹɬɧɵɟ ɰɟɧɬɪɵ ɷɥɟɤɬɪɨɮɢɥɶɧɨɣ ɚɬɚɤɢ.
7. Ɉɰɟɧɤɚ ɪɚɫɬɜɨɪɢɦɨɫɬɢ.
ɗɥɟɤɬɪɢɱɟɫɤɢɣ ɞɢɩɨɥɶɧɵɣ ɦɨɦɟɧɬ ɦɨɥɟɤɭɥɵ CClF3 ɢɦɟɟɬ ɧɟɛɨɥɶɲɭɸ ɜɟɥɢɱɢɧɭ 0.27 D.
ȼɵɜɨɞ: Ɇɨɥɟɤɭɥɚ CClF3 ɪɚɫɬɜɨɪɢɦɚ ɩɪɟɢɦɭɳɟɫɬɜɟɧɧɨ ɜ ɫɥɚɛɨ ɩɨɥɹɪɧɵɯ ɪɚɫɬɜɨɪɢɬɟɥɹɯ.