Õëîðèä ìàðãàíöà

MnCl(ã). Òåðìîäèíàìè÷åñêèå ñâîéñòâà ãàçîîáðàçíîãî õëîðèäà ìàðãàíöà â ñòàíäàðòíîì ñîñòîÿíèè ïðè òåìïåðàòóðàõ 100 - 6000 Ê ïðèâåäåíû â òàáë. MnCl.

 òàáë. Mn.4 ïðåäñòàâëåíû ìîëåêóëÿðíûå ïîñòîÿííûå, èñïîëüçîâàííûå äëÿ ðàñ÷åòà òåðìîäèíàìè÷åñêèõ ôóíêöèé MnCl.

Ýëåêòðîííûé ñïåêòð MnCl âïåðâûå íàáëþäàëñÿ â èñïóñêàíèè âûñîêî÷àñòîòíîãî ðàçðÿäà íàä ñîëüþ MnCl2 [39MES].  ñïåêòðå îáíàðóæåíû ñèñòåìû ïîëîñ â ðàéîíàõ 4800-5100Å, 4250-4600Å è 3500-3950Å.

Ñèñòåìà 3500-3950Å ÷àñòè÷íî ïðîàíàëèçèðîâàíà â [39MES], ïîëó÷åíû êîëåáàòåëüíûå êîíñòàíòû. Ïîçæå ñèñòåìà íàáëþäàëàñü â [43MUL], ïðè÷åì êàê â ðàçðÿäå, òàê è â ñïåêòðå ïîãëîùåíèÿ ïàðîâ íàä MnCl2 ïðè òåìïåðàòóðàõ 1500-1700Ñ. Àíàëèç ñèñòåìû ïî êàíòàì [48BAC, 49RAO2, 55HAY/NEV3] ïîêàçàë, ÷òî îíà îáðàçîâàíà ïåðåõîäîì 7Π - 7Σ.

Ñèñòåìà 4250-4600Å â [39MES] íå ïðîàíàëèçèðîâàíà, â äðóãèõ ðàáîòàõ äàííàÿ ñèñòåìà íå íàáëþäàëàñü, åå îòíåñåíèå ê MnCl íåäîñòîâåðíî.

Ñèñòåìà 4800-5100Å áûëà èññëåäîâàíà â ñïåêòðå èñïóñêàíèÿ â ðàáîòå [55HAY]. Àíàëèç ïî êàíòàì ïîêàçàë, ÷òî ïîëîñû íà ýòîì ó÷àñòêå ñïåêòðà ïðèíàäëåæàò äâóì ñèñòåìàì, ñèììåòðèÿ êîìáèíèðóþùèõ ýëåêòðîííûõ ñîñòîÿíèé òî÷íî íå óñòàíîâëåíà.

Åùå äâå ñèñòåìû ïîëîñ MnCl îáíàðóæåíû â ñïåêòðå èñïóñêàíèÿ â èíôðàêðàñíîé îáëàñòè. Ýòî ñèñòåìû 8180-9150Å [55HAY/NEV2, 92LAU] è 1001íì [92LAU].

 ðàáîòå [55HAY/NEV2] âûïîëíåí êîëåáàòåëüíûé àíàëèç ñèñòåìû 8180-9150Å ïî êàíòàì, ñèììåòðèÿ êîìáèíèðóþùèõ ñîñòîÿíèé òî÷íî íå óñòàíîâëåíà.  [92LAU] ÷àñòè÷íî ðàçðåøåíà âðàùàòåëüíàÿ ñòðóêòóðà ïîëîñ äàííîé ñèñòåìû. Ñïåêòð ñìîäåëèðîâàí (ïîäáîðîì êîíñòàíò âåðõíåãî è íèæíåãî ñîñòîÿíèÿ) êàê ïåðåõîä 5Σ - 5Σ.

Ñèñòåìà 1001íì íå ïðîàíàëèçèðîâàíà.

 ñïåêòðå ïîãëîùåíèÿ íàáëþäàëàñü åùå îäíà ñèñòåìà ïîëîñ MnCl â ðàéîíå 2400-2500Å, êîòîðàÿ àíàëîãè÷íà ñèñòåìå 2350-2500Å ìîëåêóëû MnF, âûïîëíåí àíàëèç êîëåáàòåëüíîé ñòðóêòóðû ñèñòåìû ïî êàíòàì [48BAC].

Ñïåêòð ýëåêòðîííîãî ïàðàìàãíèòíîãî ðåçîíàíñà MnCl â ìàòðèöå èç àðãîíà ïðè 4ºK ïîëó÷åí â ðàáîòå [82BAU/VAN]. Îïðåäåëåíû ïàðàìåòðû ñâåðõòîíêîãî âçàèìîäåéñòâèÿ â îñíîâíîì ñîñòîÿíèè 7Σ.

×èñòî âðàùàòåëüíûé ñïåêòð MnCl â îñíîâíîì ñîñòîÿíèè X7Σ+ ïîëó÷åí â ðàáîòå [2005HAL/ZIU]. Ñ î÷åíü âûñîêîé òî÷íîñòüþ èçìåðåíà òîíêàÿ è ñâåðõòîíêàÿ ñòðóêòóðà âðàùàòåëüíûõ ïåðåõîäîâ â êîëåáàòåëüíûõ ñîñòîÿíèÿõ υ = 0, 1 è 2.

Ab initio ðàñ÷åòû MnCl âûïîëíåíû â ðàáîòàõ [88DAV/YOU, 2005NIE/ALL].  îáåèõ ðàáîòàõ ðàññ÷èòàíû ïàðàìåòðû îñíîâíîãî ñîñòîÿíèÿ. Ðàñ÷åòû âîçáóæäåííûõ ñîñòîÿíèé â ëèòåðàòóðå îòñóòñòâóþò.

 ðàñ÷åò òåðìîäèíàìè÷åñêèõ ôóíêöèé áûëè âêëþ÷åíû: à) îñíîâíîå ñîñòîÿíèå X7Σ+; á) ýêñïåðèìåíòàëüíî íàáëþäàâøèåñÿ âîçáóæäåííûå ñîñòîÿíèÿ; â) íå íàáëþäàâøèåñÿ ñîñòîÿíèÿ ñ îöåíåííîé ýíåðãèåé äî 40000 ñì-1.

Êîëåáàòåëüíûå ïîñòîÿííûå îñíîâíîãî ñîñòîÿíèÿ MnCl ïîëó÷åíû â [39MES, 43MUL, 48BAC, 49RAO, 55HAY/NEV3]. Èìåþòñÿ ñóùåñòâåííûå ðàñõîæäåíèÿ â âåëè÷èíå ωexe. Ñïðàâî÷íèê [84ÕÜÞ/ÃÅÐ] ïðèâîäèò òîëüêî âåëè÷èíó ΔG1/2 = 382.4 ñì-1. Çíà÷åíèÿ ωe è ωexe, ïðåäñòàâëåííûå â òàáë. Mn.4, ðàññ÷èòàíû ïî ôîðìóëå (1.67) ñ èñïîëüçîâàíèåì óêàçàííîé âåëè÷èíû ΔG1/2 è ïðèíÿòîãî çíà÷åíèÿ D0 = 27920 ñì‑1 .

Âðàùàòåëüíûå ïîñòîÿííûå îñíîâíîãî ñîñòîÿíèÿ MnCl ïîëó÷åíû â ðàáîòå [2005HAL/ZIU].

Ñèñòåìû ïîëîñ, íàáëþäàâøèåñÿ â ñïåêòðå èñïóñêàíèÿ, íî íå íàáëþäàâøèåñÿ â ñïåêòðå ïîãëîùåíèÿ, èñõîäÿ èç àíàëîãèè ñ MnF, èíòåðïðåòèðîâàíû êàê êâèíòåòíûå ïåðåõîäû ñ îáùèì íèæíèì ñîñòîÿíèåì a5Σ+. Ýíåðãèÿ a5Σ+, êàê è â MnF, ïðèíÿòà ðàâíîé 3500 ñì‑1, ïîãðåøíîñòü óâåëè÷åíà äî ±1500 ñì‑1. Ýíåðãèè âåðõíèõ ñîñòîÿíèé ïîëó÷åíû ïðèáàâëåíèåì âåëè÷èí ν = 10047.8 ñì‑1 [92LAU], T0(c5Σ+) = 11398.91 ñì‑1 [92LAU], νe = 20115.4 ñì‑1 è νe ~ 19900 ñì‑1 [55HAY].

Äëÿ ñîñòîÿíèé A7Π è B(7Σ+) ïðèâåäåíû çíà÷åíèÿ Te èç [84ÕÜÞ/ÃÅÐ].

Êîëåáàòåëüíûå è âðàùàòåëüíûå êîíñòàíòû âîçáóæäåííûõ ñîñòîÿíèé MnCl ïðèâåäåíû ïî äàííûì [92LAU] (a5Σ+, c5Σ+) è [84ÕÜÞ/ÃÅÐ] (A7Π, B(7Σ+)).  ðàñ÷åòå òåðìîäèíàìè÷åñêèõ ôóíêöèé ýòè êîíñòàíòû íå èñïîëüçîâàëèñü è äàíû â òàáë. Mn.4 äëÿ ñïðàâêè.

Ýíåðãèè ñîñòîÿíèé, íå íàáëþäàâøèõñÿ â ýëåêòðîííîì ñïåêòðå, îöåíåíû íà îñíîâå èîííîé ìîäåëè Mn+X-, àíàëîãè÷íî òîìó, êàê ýòî ñäåëàíî äëÿ ìîëåêóëû MnF. Ñõîäñòâî ýëåêòðîííûõ ñïåêòðîâ äâóõ ìîëåêóë ïîçâîëÿåò ïðåäïîëîæèòü, ÷òî â MnCl, òàêæå êàê è â MnF, ÷åòûðå êîíôèãóðàöèè èîíà Mn+ äàþò ñîñòîÿíèÿ ñ ýíåðãèåé íèæå 40000 ñì‑1: 3d54s, 3d6, 3d44s2, 3d54p.

Êîíôèãóðàöèÿ 3d54s äàåò ñîñòîÿíèÿ X7Σ+ è a5Σ+, êîòîðûå ñîîòâåòñòâóþò äâóì íèæíèì òåðìàì èîíà 7S è 5S [71MOO]. Íå íàáëþäàâøèåñÿ ñîñòîÿíèÿ ñîîòâåòñòâóþò êîìïîíåíòàì ðàñùåïëåíèÿ â ïîëå ëèãàíäà òåðìîâ 5G, 5P è ò.ä., êîòîðûå â èîíå ëåæàò âûøå 27000 ñì‑1. Ýòè ñîñòîÿíèÿ ðàñïðåäåëåíû ïî óðîâíÿì ýíåðãèè (ñèíòåòè÷åñêèì ñîñòîÿíèÿì) â ñîîòâåòñòâèè ñ ðàñïîëîæåíèåì òåðìîâ â èîíå [71MOO]. Ðàñùåïëåíèå â ïîëå ëèãàíäà íå ó÷èòûâàëîñü.

Êîíôèãóðàöèÿ 3d6 ïðåäñòàâëåíà ñîñòîÿíèÿìè b(c5Σ+) è c(5Πi), êîòîðûå ñîîòâåòñòâóþò äâóì èç òðåõ êîìïîíåíò ðàñùåïëåíèÿ òåðìà 5D, íèæíåãî òåðìà äàííîé êîíôèãóðàöèè. Ýíåðãèÿ òðåòüåé, íå íàáëþäàâøåéñÿ, êîìïîíåíòû 5Δ îöåíåíà â 16000±2000 ñì-1. Îñòàëüíûå ñîñòîÿíèÿ ñîîòâåòñòâóþò êîìïîíåíòàì ðàñùåïëåíèÿ òðèïëåòíûõ òåðìîâ 3P, 3H è ò.ä., êîòîðûå â èîíå ëåæàò áîëåå ÷åì íà 15000 ñì‑1 âûøå òåðìà 5D. Ýòè ñîñòîÿíèÿ ðàñïðåäåëåíû ïî ñèíòåòè÷åñêèì ñîñòîÿíèÿì (óðîâíÿì ýíåðãèè) â ñîîòâåòñòâèè ñ ýíåðãèåé òåðìîâ â ïîëå ëèãàíäà. Ýíåðãèÿ òåðìîâ â ïîëå ëèãàíäà ðàññ÷èòûâàëàñü êàê ýíåðãèÿ òåðìà â èîíå îòíîñèòåëüíî òåðìà 5D [71MOO] ïëþñ ýíåðãèÿ ñîñòîÿíèÿ b5Πi. Ðàñùåïëåíèå òåðìîâ â ïîëå ëèãàíäà íå ó÷èòûâàëîñü.

Ê êîíôèãóðàöèè 3d44s2 îòíåñåíû äâà ñîñòîÿíèÿ îêîëî 23500 ñì-1, êîòîðûå ÿâëÿþòñÿ ïðåäïîëîæèòåëüíî 5Π è 5Σ êîìïîíåíòàìè ðàñùåïëåíèÿ íèæíåãî òåðìà êîíôèãóðàöèè, òåðìà 5D. Ýíåðãèÿ íå íàáëþäàâøåéñÿ êîìïîíåíòû ðàñùåïëåíèÿ - 5Δ, îöåíåíà â 23000±2000 ñì-1. Äàííûå î äðóãèõ òåðìàõ êîíôèãóðàöèè â [71MOO] îòñóòñòâóþò.

Êîíôèãóðàöèÿ Mn+(3d54p) ïðåäñòàâëåíà ñîñòîÿíèåì A7Π, êîòîðîå ñîîòâåòñòâóåò íèæíåé êîìïîíåíòå ðàñùåïëåíèÿ òåðìà 7P. Ñòàòèñòè÷åñêèé âåñ íå íàáëþäàâøåéñÿ âåðõíåé êîìïîíåíòû ðàñùåïëåíèÿ - 7Σ+, îòíåñåí ê óðîâíþ ýíåðãèè 35000 ñì-1. Ñòàòèñòè÷åñêèé âåñ ñëåäóþùåãî òåðìà 5P ðàñïðåäåëåí ïî óðîâíÿì ýíåðãèè 35000 ñì-1 (5Π) è 40000 ñì-1 (5Σ+). Äðóãèå òåðìû êîíôèãóðàöèè äàþò ñîñòîÿíèÿ âûøå 40000 ñì-1.

Òåðìîäèíàìè÷åñêèå ôóíêöèè MnCl(ã) áûëè âû÷èñëåíû ïî óðàâíåíèÿì (1.3) - (1.6), (1.9), (1.10), (1.93) - (1.95). Çíà÷åíèÿ Qâí è åå ïðîèçâîäíûõ ðàññ÷èòûâàëèñü ïî óðàâíåíèÿì (1.90) - (1.92) ñ ó÷åòîì òðèíàäöàòè âîçáóæäåííûõ ñîñòîÿíèé â ïðåäïîëîæåíèè, ÷òî Qêîë.âð(i) = (pi/pX)Qêîë.âð(X). Êîëåáàòåëüíî-âðàùàòåëüíàÿ ñòàòèñòè÷åñêàÿ ñóììà ñîñòîÿíèÿ X7Σ+ è åå ïðîèçâîäíûå âû÷èñëÿëèñü ïî óðàâíåíèÿì (1.70) - (1.75) íåïîñðåäñòâåííûì ñóììèðîâàíèåì ïî êîëåáàòåëüíûì óðîâíÿì è èíòåãðèðîâàíèåì ïî âðàùàòåëüíûì óðîâíÿì ýíåðãèè ñ ïîìîùüþ óðàâíåíèÿ òèïà (1.82).  ðàñ÷åòàõ ó÷èòûâàëèñü âñå óðîâíè ýíåðãèè ñî çíà÷åíèÿìè J < Jmax,v, ãäå Jmax,v íàõîäèëîñü èç óñëîâèé (1.81). Êîëåáàòåëüíî-âðàùàòåëüíûå óðîâíè ñîñòîÿíèÿ X7Σ+ âû÷èñëÿëèñü ïî óðàâíåíèÿì (1.65), çíà÷åíèÿ êîýôôèöèåíòîâ Ykl â ýòèõ óðàâíåíèÿõ áûëè ðàññ÷èòàíû ïî ñîîòíîøåíèÿì (1.66) äëÿ èçîòîïè÷åñêîé ìîäèôèêàöèè, ñîîòâåòñòâóþùåé åñòåñòâåííîé ñìåñè èçîòîïîâ õëîðà èç ìîëåêóëÿðíûõ ïîñòîÿííûõ 55Mn35Cl, ïðèâåäåííûõ â òàáë. Mn.4. Çíà÷åíèÿ êîýôôèöèåíòîâ Ykl, à òàêæå âåëè÷èíû vmax è Jlim ïðèâåäåíû â òàáë. Mn.5.

Îñíîâíûå ïîãðåøíîñòè ðàññ÷èòàííûõ òåðìîäèíàìè÷åñêèõ ôóíêöèé MnCl(ã) ïðè òåìïåðàòóðàõ 1000 - 6000 Ê îáóñëîâëåíû ìåòîäîì ðàñ÷åòà è íåîïðåäåëåííîñòüþ ýíåðãèè ñîñòîÿíèÿ a5Σ+. Ïîãðåøíîñòè â çíà÷åíèÿõ Φº(T) ïðè T = 298.15, 1000, 3000 è 6000 Ê îöåíèâàþòñÿ â 0.05, 0.4, 1.4 è 1.6 Äæ×K‑1×ìîëü‑1, ñîîòâåòñòâåííî.

Òåðìîäèíàìè÷åñêèå ôóíêöèè MnCl(ã) ðàíåå âû÷èñëÿëèñü ñ ó÷åòîì âîçáóæäåííûõ ñîñòîÿíèé äî 6000 Ê [85ÁÅÐ/ÃÓÐ]. Ðàñõîæäåíèÿ ñ äàííûìè [85ÁÅÐ/ÃÓÐ] ëåæàò â ïðåäåëàõ ïîãðåøíîñòè ðàñ÷åòîâ, â âåëè÷èíå Φº(T) îíè ñîñòàâëÿþò 0.05 Äæ×K‑1×ìîëü‑1 ïðè 1000 Ê è 1.2 Äæ×K‑1×ìîëü‑1 ïðè 6000 Ê. Ðàñõîæäåíèÿ îáóñëîâëåíû ãëàâíûì îáðàçîì èñïîëüçîâàíèåì â íàñòîÿùåé ðàáîòå áîëåå íèçêîé îöåíêè ýíåðãèè ñîñòîÿíèÿ a5Σ+.

Êîíñòàíòà ðàâíîâåñèÿ ðåàêöèè MnCl(ã) = Mn(ã) + Cl(ã) ðàññ÷èòàíà íà îñíîâàíèè ïðèíÿòîãî çíà÷åíèÿ ýíåðãèè äèññîöèàöèè MnCl:

D°0(MnCl) = 334 ± 6 êÄæ×ìîëü‑1 = 27920 ± 500 ñì‑1.

 ðàáîòå [95HIL] áûëî âûïîëíåíî ìàññ-ñïåêòðîìåòðè÷åñêîå èçìåðåíèå êîíñòàíò ðàâíîâåñèÿ Mn(ã) + MnCl2(ã) = 2MnCl(ã). Ïîëó÷åíû 2 çíà÷åíèÿ êîíñòàíòû ðàâíîâåñèÿ äëÿ Ò = 1512 è 1567 Ê. Îáðàáîòêà ýòèõ ðåçóëüòàòîâ ñ èñïîëüçîâàíèåì III çàêîíà òåðìîäèíàìèêè ïðèâîäèò ê çíà÷åíèÿì DrH°(0) = 115.8 ± 10 êÄæ×ìîëü‑1 è D°0(MnCl) = 334 ± 6 êÄæ×ìîëü‑1 . Ýòî çíà÷åíèå è ïðèíèìàåòñÿ â äàííîì äîêóìåíòå.

Ýêñïåðèìåíòû [68MUR/DAD] ïî ïåðåíîñó ìàðãàíöà ïàðàìè MnCl2 (8 èçìåðåíèé â èíòåðâàëå òåìïåðàòóð 1243 ‑ 1413 Ê) ïðèâîäÿò äëÿ ðàâíîâåñèÿ Mn(ê, æ) + MnCl2(ã) = 2MnCl(ã) ê çíà÷åíèÿì DrH°(0) = 292.5 ± 6.3 (III çàêîí) è 224 ± 22 (II çàêîí) êÄæ×ìîëü‑1 . (D°0(MnCl) = 388 ± 5 (III) è 420 ± 11 (II)êÄæ×ìîëü‑1 ). Ïðè÷èíû íåñîîòâåòñòâèÿ íå ÿñíû.

 ðàáîòå [61BUL/PHI] ïðèâîäèòñÿ âåëè÷èíà D°0(MnCl) = 356 ± 8 êÄæ×ìîëü‑1 , îñíîâàííàÿ íà âûïîëíåííûõ àâòîðàìè ðåçóëüòàòàõ èçìåðåíèé êîíñòàíò ðàâíîâåñèÿ ñ ó÷àñòèåì MnCl, ïîëó÷åííûõ ìåòîäîì ôîòîìåòðèè ïëàìåí, îäíàêî, ìíîãèå ïðåäïîëîæåíèÿ àâòîðîâ ðàáîòû îòíîñèòåëüíî òèïîâ ïðîäóêòîâ, ïðèñóòñòâîâàâøèõ â èçó÷åííûõ ñèñòåìàõ, à òàêæå îòíîñèòåëüíî èñïîëüçîâàííûõ â ðàñ÷åòàõ ìîëåêóëÿðíûõ ïîñòîÿííûõ òðóäíî ïðîâåðÿåìû.

Êâàíòîâî-ìåõàíè÷åñêèå âû÷èñëåíèÿ äîâîëüíî âûñîêîãî â òåîðåòè÷åñêîì îòíîøåíèè óðîâíÿ (CCSD(T)) ïðèâîäÿò ê áëèçêîìó çíà÷åíèþ: D°0(MnCl) = 333 êÄæ×ìîëü‑1 [2005NIE/ALL]. Íàøè ñîáñòâåííûå êâàíòîâî-ìåõàíè÷åñêèå âû÷èñëåíèÿ (òàêæå CCSD(T), íå îïóáëèêîâàíî) ïðèâîäÿò ê çíà÷åíèþ: D°0(MnCl) = 345 ± 21 êÄæ×ìîëü‑1 .  ýòèõ âû÷èñëåíèÿõ èñïîëüçîâàíà ïðîöåäóðà îöåíêè äîñòîâåðíîñòè ðåçóëüòàòà, íàçâàííàÿ íàìè «èäåîëîãèåé ãðóïï ñöåïëåíèÿ» [2006ÃÓÑ/ÈÎÐ].

Ïðèíÿòîìó çíà÷åíèþ ñîîòâåòñòâóþò âåëè÷èíû:

DfH°(MnCl, ã, 0) = 68.922 ± 6.3 êÄæ×ìîëü‑1 è

DfH°(MnCl, ã, 298.15) = 68.885 ± 6.3 êÄæ×ìîëü‑1 .

Àâòîðû

Ãóñàðîâ À.Â. a-gusarov@yandex.ru

Êóëèêîâ À.Í. aleksej-kulikov@km.ru

Êëàññ òî÷íîñòè
5-E

Õëîðèä ìàðãàíöà MnCl(ã)

 Òàáëèöà 1465
MNCL=MN+CL      DrH°  =  334.000 êÄæ × ìîëü-1
T C°p (T) F° (T) S° (T) H° (T)  -  H° (0) lg K° (T) T
K Äæ × K-1 × ìîëü-1 êÄæ × ìîëü-1 K
100.000
200.000
298.150
300.000
400.000
500.000
600.000
700.000
800.000
900.000
1000.000
1100.000
1200.000
1300.000
1400.000
1500.000
1600.000
1700.000
1800.000
1900.000
2000.000
2100.000
2200.000
2300.000
2400.000
2500.000
2600.000
2700.000
2800.000
2900.000
3000.000
3100.000
3200.000
3300.000
3400.000
3500.000
3600.000
3700.000
3800.000
3900.000
4000.000
4100.000
4200.000
4300.000
4400.000
4500.000
4600.000
4700.000
4800.000
4900.000
5000.000
5100.000
5200.000
5300.000
5400.000
5500.000
5600.000
5700.000
5800.000
5900.000
6000.000
30.167
33.772
35.544
35.565
36.409
36.887
37.240
37.572
37.924
38.299
38.687
39.071
39.438
39.779
40.088
40.364
40.608
40.822
41.012
41.183
41.340
41.489
41.634
41.780
41.931
42.090
42.260
42.444
42.642
42.857
43.088
43.337
43.603
43.887
44.187
44.504
44.836
45.184
45.545
45.920
46.307
46.706
47.114
47.533
47.959
48.394
48.834
49.280
49.731
50.185
50.640
51.097
51.554
52.009
52.462
52.911
53.354
53.792
54.221
54.641
55.051
188.352
209.049
221.567
221.765
231.132
238.589
244.797
250.122
254.789
258.947
262.700
266.122
269.271
272.188
274.907
277.455
279.852
282.117
284.264
286.304
288.249
290.108
291.887
293.594
295.234
296.813
298.335
299.805
301.225
302.601
303.934
305.227
306.483
307.705
308.893
310.051
311.180
312.281
313.357
314.408
315.436
316.442
317.428
318.394
319.340
320.269
321.181
322.077
322.958
323.823
324.674
325.512
326.337
327.150
327.950
328.739
329.518
330.285
331.042
331.790
332.528
217.643
239.742
253.603
253.823
264.184
272.363
279.121
284.886
289.926
294.414
298.469
302.175
305.590
308.761
311.720
314.495
317.108
319.577
321.916
324.138
326.254
328.275
330.208
332.062
333.843
335.558
337.212
338.811
340.358
341.858
343.315
344.732
346.112
347.458
348.772
350.058
351.316
352.549
353.759
354.947
356.114
357.263
358.393
359.506
360.604
361.687
362.755
363.810
364.852
365.883
366.901
367.908
368.905
369.891
370.868
371.834
372.792
373.740
374.679
375.610
376.531
2.929
6.139
9.552
9.617
13.221
16.887
20.594
24.335
28.109
31.920
35.770
39.658
43.583
47.544
51.538
55.561
59.610
63.681
67.773
71.883
76.010
80.151
84.307
88.478
92.663
96.864
101.082
105.317
109.571
113.846
118.143
122.464
126.811
131.185
135.589
140.023
144.490
148.991
153.528
158.101
162.712
167.362
172.053
176.786
181.560
186.378
191.239
196.145
201.095
206.091
211.132
216.219
221.352
226.530
231.754
237.022
242.336
247.693
253.094
258.537
264.022
-171.1680
-83.5131
-54.5813
-54.2173
-39.5376
-30.7117
-24.8161
-20.5971
-17.4273
-14.9579
-12.9796
-11.3589
-10.0068
-8.8616
-7.8792
-7.0272
-6.2812
-5.6227
-5.0370
-4.5129
-4.0410
-3.6139
-3.2256
-2.8710
-2.5459
-2.2468
-1.9707
-1.7150
-1.4776
-1.2566
-1.0503
-.8574
-.6764
-.5065
-.3465
-.1957
-.0532
   .0816
   .2093
   .3305
   .4457
   .5553
   .6598
   .7595
   .8547
   .9459
1.0331
1.1167
1.1970
1.2741
1.3483
1.4197
1.4885
1.5549
1.6190
1.6809
1.7408
1.7988
1.8550
1.9094
1.9622
100.000
200.000
298.150
300.000
400.000
500.000
600.000
700.000
800.000
900.000
1000.000
1100.000
1200.000
1300.000
1400.000
1500.000
1600.000
1700.000
1800.000
1900.000
2000.000
2100.000
2200.000
2300.000
2400.000
2500.000
2600.000
2700.000
2800.000
2900.000
3000.000
3100.000
3200.000
3300.000
3400.000
3500.000
3600.000
3700.000
3800.000
3900.000
4000.000
4100.000
4200.000
4300.000
4400.000
4500.000
4600.000
4700.000
4800.000
4900.000
5000.000
5100.000
5200.000
5300.000
5400.000
5500.000
5600.000
5700.000
5800.000
5900.000
6000.000

M = 90.391
DH° (0)  =  68.922 êÄæ × ìîëü-1
DH° (298.15 K)  =  68.885 êÄæ × ìîëü-1
S°ÿä  =  31.027 Äæ × K-1 × ìîëü-1

F°(T)  =  350.962646484 + 38.6462783813 lnx - 0.000941602513194 x-2 + 0.242386966944 x-1 - 27.8560333252 x + 139.3152771 x2 - 213.716705322 x3
(x = T ×10-4;   298.15  <  T <   1500.00 K)

F°(T)  =  376.579162598 + 56.6203842163 lnx - 0.0599974170327 x-2 + 2.76781892776 x-1 - 57.2032852173 x + 50.7159118652 x2 - 16.2511367798 x3
(x = T ×10-4;   1500.00  <  T <   6000.00 K)

15.12.08

Òàáëèöà Mn.4. Ìîëåêóëÿðíûå ïîñòîÿííûå Mn2, MnH, MnF, MnCl, MnBr, MnI, MnO è MnS.

Ìîëåêóëà

Ñîñòîÿíèå

Te

we

wexe

Be

a1×102

De×106

re

ñì‑1

Å

55Mn2

X 1Σ+g à

0

51

0.7 á

0.05 â

0.08 ã

0.2 ä

3.5(3)

3Σ+u

10 å

5Σ+g

30 å

7Σ+u

60 å

9Σ+g

100 å

11Σ+u

150 å

11Πu

8500 æ

205

1.1 á

0.091 â

0.06 ã

0.07 ä

2.6

55Mn1H

X 7Σ+ à

0

1546.845

27.597 á

5.68568

16.020 á

305.4 á

1.73086

a 5Σ+

1725 â

1720

70

6.44912

19.239

404.06 â, æ

1.625185

b5Πi

11155 â, ã

6.3953 â

366.7 â

1.63197 â

c 5Σ+

13564 â

1624 â

6.3082

17.82

320.56 â

1.64320

d5D

13000 è

1582 ê

1.664 ê

A7Π

17597 ä

1623 â

33

6.346098 â

18.7

372.04 â

1.638324 â

B 7Σ+

20000 è

2.5 ë

d5Πi

22606 â, å

1638

6.2045

16.45

356.0 â, ç

1.65691

e 5Σ+

24056 â

1660

5.5367 â

199.4 â

1.75399 â

55Mn19F

X 7Σ+ à

0

624.2

3.2

0.354318223

0.2641034

0.461635 á

1.83584

a 5Σ+

3500 ã

645.92

3.22

0.374641

0.2758

0.5134

1.785356

b5Πi

15600 â, ä

630.54

3.564

0.37342

0.2443

1.7883

c 5Σ+

18000 â

597.38

3.15

0.3607915

0.30558

0.53639

1.819300

d5Πi

23300 â, å

640.0

3.6

0.363007 á

1.81374 á

e 5Σ+

23700 â

637.1

1.9

A7Π

28525.9 æ

648.0

1.6

0.37175

0.286

1.7923

B(7Σ+)

41231.5

637.2

4.46

55Mn 35Cl

X 7Σ+ à

0

385.0 ä

1.3 ä

0.1579142

0.080656

0.1055555 á

2.2351512

a 5Σ+

3500 ã

402.24

1.35

0.18814

0.089

0.1635

2.0477

b(5Πi)

13550 â

c 5Σ+

14900 â

395.17

1.56

0.18456

0.161

2.0648

(d5Πi)

23400 â

378

(e 5Σ+)

23600 â

385

A7Π

27005.0 å

407.9 á

B(7Σ+)

40807

320 á

55Mn 79Br

X 7Σ+ à

0

286.7

0.8

0.0896 á

0.0334 ä

0.035 ä

2.41 ã

a 5Σ+

3500 ã

295.9

1.6

b( 5Σ+)

14200 â

295.6

0.62

c(5Πi)

14200 â

290.4

0.13

(d 5Σ+)

23200 â

(e5Πi)

23500 â

286.6

1.4

A7Π

26303.7 å

302.3

0.6

55Mn 127I

X 7Σ+ à

0

240

0.66 â

0.065 á

0.023 ä

0.019 å

2.6 ã

A(7Π)

25000

55Mn 16O

X 6Σ+ à

0

843.6 á

5.6 á

0.503248

0.4061

0.720

1.64439

(6Π)

8600 å

(4Π)

8700 å

(660)

(4Σ+)

11700 å

920

4Π

14000 æ

4Σ

16000 æ

A 6Σ+

17949

762.75

9.60

0.45969 â

0.36 ã

2.04 â

1.714 ä

4Σ

18000 æ

8Π

18000 ç

6Π

20000 ç

4Π

20000 æ

4Δ

21000 ç

8Σ+

23000 ç

6Δ

25000 ç

6Σ+

28000 ç

4Π

31000 ç

6Π

31000 ç

6Σ+

33000 ç

4Σ+

34000 ç

55Mn32S

X 6Σ+ à

0

491.051

1.861

0.19544

0.096

0.115

2.06588

(4Π)

6050 á

6Π

8600 â

4Σ+

11700 â

4Π

14000 â

4Σ

16000 â

4Σ

18000 â

8Π

18000 â

A 6Σ+

18917.37

371.50

1.30

0.17794 ã

0.17 ã

6Π

20000 â

4Π

20000 â

4Δ

21000 â

B(6Σ+)

22319.8

466.7

2.1

8Σ+

23000 â

6Δ

25000 â

6Σ+

28000 â

4Π

31000 â

6Π

31000 â

6Σ+

33000 â

4Σ+

34000 â

Ïðèìå÷àíèÿ: âñå ïîñòîÿííûå íèæå äàíû â ñì-1.

Mn2 a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

10000

15000

20000

pi

158

264

108

á âû÷èñëåíî ïî ôîðìóëå 1.67; â âû÷èñëåíî ÷åðåç re ïî ôîðìóëå 1.38; ã âû÷èñëåíî ïî ôîðìóëå 1.69; ä âû÷èñëåíî ïî ôîðìóëå 1.68;

å âû÷èñëåíî ïðè çíà÷åíèè îáìåííîãî ïàðàìåòðà J=10±2 [91KIR/BIE]; æ îöåíêà, ñì. òåêñò

MnH a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

25000

27000

30000

34000

37000

40000

pi

45

57

100

24

15

56

á ïî äàííûì [2005GOR/APP] Y30 = -0.309037 ñì‑1, 104×Y21 = -1.200, 104×Y31 = -3.0252, 106×Y12 = 1.397, 107×Y22 = -2.823, 107×Y32 = -1.225; 109×Y03 = 9.4670; 109×Y13 = -1.551; 1012×Y04 = 1.360; 1013×Y14 = 9.16; â êîíñòàíòû äëÿ óðîâíÿ v = 0, T0, DG1/2; ã A0 = -62.308; ä A0 = 40.51878; å A0 = -22.92; æ β·106 = 2.68; ç β·105 = 1.67;

è îöåíêà ñ èñïîëüçîâàíèåì ðåçóëüòàòîâ [89LAN/BAU]; ê ðàñ÷åò [89LAN/BAU]; ë èç ãðàôèêà ïîòåíöèàëüíûõ êðèâûõ [89LAN/BAU]

MnF a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

18000

23000

27500

30000

35000

40000

pi

10

10

45

57

126

35

á êîíñòàíòû äëÿ óðîâíÿ v = 0; â ñì. òåêñò; ã îöåíêà; ä A0 = -63.1183; å A = -78.2661; æ Ae = 36.596;

MnCl a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

16000

23000

27500

30000

35000

40000

pi

10

10

45

105

93

20

á êîíñòàíòû äëÿ óðîâíÿ v = 0, DG1/2; â ñì. òåêñò; ã îöåíêà; ä ðàññ÷èòàíî, èñõîäÿ èç DG1/2 = 382.4 ïî ñîîòíîøåíèþ 1.67; å A = 44;

MnBr a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

16000

23000

27500

30000

35000

40000

pi

10

10

45

95

108

15

á âû÷èñëåíî ïî ôîðìóëå 1.38; â ñì. òåêñò; ã àb initio ðàñ÷åò ìåòîäîì CCSD(T); ä âû÷èñëåíî ïî ñîîòíîøåíèÿì 1.68 è 1.69; å A ~ 58

MnI a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

3500

15000

23000

27500

30000

35000

40000

pi

5

25

25

45

95

108

15

á âû÷èñëåíî ïî ôîðìóëå 1.38; â âû÷èñëåíî ïî ôîðìóëå 1.67; ã îöåíêà ïî ôîðìóëå Ãóããåíõåéìåðà [46GUG] ïðè äàííîì çíà÷åíèè we;

ä âû÷èñëåíî ïî ñîîòíîøåíèþ 1.69; å âû÷èñëåíî ïî ñîîòíîøåíèþ 1.68;

MnO a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

20000

25000

30000

35000

40000

pi

48

26

80

166

138

á âû÷èñëåíî ïî ôîðìóëå 1.67 ïðè DG1/2 = 832.408 ± 0.012 [80GOR/MER]; â B1, D1, âðàùàòåëüíàÿ ñòðóêòóðà óðîâíÿ v = 0 ñèëüíî âîçìóùåíà;

ã B1 - B0, B0 = 0.4633; ä r0, å ôîòîýëåêòðîííûé ñïåêòð àíèîíà [2000GUT/RAO], æ ðàñ÷åò [2003DAI/DEN], ç ðàñ÷åò [2000GUT/RAO]

MnS a Îöåíåííûå ýëåêòðîííûå ñîñòîÿíèÿ:

Ti

20000

25000

30000

35000

40000

pi

42

26

80

166

138

á ôîòîýëåêòðîííûé ñïåêòð àíèîíà [96ZHA/KAW]; â îöåíêà, îñíîâàííàÿ íà ñõîäñòâå ñ MnO; ã êîíñòàíòû äëÿ óðîâíÿ v = 0;

Òàáëèöà Mn.5. Çíà÷åíèÿ êîýôôèöèåíòîâ â óðàâíåíèÿõ, îïèñûâàþùèõ óðîâíè ýíåðãèè (â ñì‑1), à òàêæå çíà÷åíèÿ vmax è Jlim, ïðèíÿòûå äëÿ ðàñ÷åòà òåðìîäèíàìè÷åñêèõ ôóíêöèé Mn2, MnH, MnF, MnCl, MnBr, MnI, MnO, MnS.

Êîýôôè-öèåíòû

Mn2

MnH

MnF

MnCl

MnBr

MnI

MnO

MnS

X 1Σ+g à

11Πu

X 7Σ+ à, á

X 7Σ+ à

X 7Σ+ à

X 7Σ+ à

X 7Σ+ à

X 6Σ+ à

X 6Σ+ à

T e10-4

0

0.85

0

0

0

0

0

0

0

Y10×10-2

0.510000

2.050001

15.56329

6.247554

3.833904

2.857866

2.400001

8.435085

4.919365

Y20

-0.700001

-1.100001

-37.23409

-3.375240

-1.289153

-0.7418316

-0.6600006

-5.598786

-2.288995

Y30×103

3547.060

6.007442

-0.5752594

-3.139689

Y01×102

5.000004

9.100010

568.5265

35.43184

15.65965

8.914640

6.500006

50.31389

19.51013

Y11×104

-8.000011

-6.000009

-1601.864

-26.41036

-7.964861

-3.314670

-2.300003

-40.59680

-9.575054

Y12×106

1.396746

Y21×106

-119.9826

3.208893

Y02×107

-2.000004

-0.700001

-3053.396

-4.616355

-1.038008

-0.3464653

-0.1900004

-7.196879

-1.146018

Y03×1012

-1.484884

-0.118289

9464.933

-0.5913955

-0.05949802

-0.01222040

-0.007415519

-1.509901

-0.1284487

(a0 = De)×10-4

1.246929

a2×103

1.167603

a3×107

-3.560246

a4×1011

3.954078

vmax

35

92

14

166

148

161

181

74

90

Jlim

183

432

66

437

570

698

769

333

489

Ïðèìå÷àíèå. à ýíåðãèè âîçáóæäåííûõ ñîñòîÿíèé ïðèâåäåíû â òàáëèöå Mn.4;

á Y40×101 = -5.895856, Y50×102 = 2.025045, Y31×104 = -3.024650, Y22×107 = -2.822384, Y32×107 = -1.224688, Y13×109 = -1.550605, Y04×1013 = -8.335066

Ñïèñîê ëèòåðàòóðû

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