Table 1
Observed Stark Resonances in PH3 for E Levels and A Levels with Small A 1 A 2 Splittings
Assignment Resonant Field (V/cm)
M ′M ″E obs ΔE 12 C16 O2 10P (28) QP (6, 4) −5 −4 26774 20 −4 −3 30876 −3 −3 −2 36508 −2 −2 −1 44632 −23 −1 0 57495 11 10P (6) QP (4, 3) 3 2 10107 −9 2 1 12997 −2 1 0 18190 10 0 −1 30199 −2 3 4 30332 0 10R (8) QQ (15, 8) M + 1M 48920a 10R (14) PP (13, 13) 10 9 35287 −48 8 7 38862 −15 7 6 40929 2 6 5 43225 19 5 4 45791 38 4 3 48650 30 3 2 51875 4 2 1 55570 −17 1 0 59858 −18 10R (30) QQ (9, 5) M − 1M 45107a 10R (30) PP (13, 11) 7 6 21441 11 6 5 22488 14 5 4 23640 15 4 3 24891 −10 3 2 26316 −8 2 1 27918 1 1 0 29716 0 0 −1 31757 −6 −1 −2 34140 27 −2 −3 36790 −48 −3 −4 40019 −18 −4 −5 43874 29 −5 −6 48439 −12 −6 −7 54151 11 10R (32) QQ (8, 4) M − 1M 9951a 10R (34) QQ (14, 12) M − 1M 2128a 10R (36) QQ (11, 9) M − 1M 54045a 10R (42) PP (12, 11) 8 7 26898 63 7 6 28254 43 6 5 29718 −18 5 4 31359 −76 4 3 33418 79 3 2 35541 52 2 1 37822 −116 1 0 40645 −103 0 −1 44026 19 −1 −2 47891 58 −2 −3 52403 13 −3 −4 57904 −3 9P (26) QR (5, 4) −4 −5 43014 27 −3 −4 49621 23 −2 −3 58547 −33 9P (26) PP (7, 7) 6 5 16792 −11 5 4 18264 14 4 3 19971 2 3 2 22024 −22 2 1 24626 20 1 0 27853 16 0 −1 32065 19 −1 −2 37717 −37 −2 −3 45929 −7 −3 −4 58655 10 9P (24) QR (5, 5) 4 5 4306 −7 3 4 4970 −6 2 3 5877 −4 1 2 7160 −26 0 1 9216 −20 6 5 12941 −13 5 4 21593 10 −3 −2 63317 4 4 3 64075 2 9P (22) RP (11, 7) 6 5 24810 19 5 4 28003 −11 10 11 29422 −24 4 3 32188 −14 9 10 34106 −1 3 2 37866 6 8 9 40520 1 2 1 45922 −6 7 8 49913 12 1 0 58369 7 9P (18) RP (10, 2) −7 −6 6807 −60 −6 −5 7704 −32 −9 −10 8595 −49 −5 −4 8815 −39 −8 −9 10023 −43 −4 −3 10303 −48 −7 −8 11981 −65 −3 −2 12437 −21 −6 −7 14966 −32 −2 −1 15645 4 −5 −6 19829 −39 −1 0 21045 32 −4 −5 29522 91 0 1 32053 39 9P (18) PP (7, 5) 5 4 41604 0 4 3 44088 −3 3 2 46896 5 2 1 50066 −3 1 0 53706 1 0 −1 57905 0 9P (8) RP (9, 5) 7 6 19816 −38 6 5 22341 14 5 4 25514 12 4 3 29731 0 8 9 30007 2 3 2 35645 6 7 8 36041 7 2 1 44469 −7 6 7 45092 −1 1 0 59136 2 5 6 60226 −2 9P (6) PP (7, 1) −6 −7 5827 −16 −5 −6 6660 14 −4 −5 7702 1 −3 −4 9144 −17 −2 −3 11357 25 −1 −2 14889 −9 0 −1 22044 0 9P (4) QR (7, 7) 6 7 48792 −4 5 6 53925 6 4 5 60239 −3 9R (6) QR (8, 8) −7 −8 44041 14 −6 −7 48019 −19 −5 −6 52855 2 −4 −5 58745 3 9R (8) RP (7, 4) 6 5 34918 −6 5 4 40293 3 4 3 47605 2 6 7 58172 0 9R (10) QR (9, 7) −7 −8 6490 −22 −6 −7 7064 −14 −5 −6 7738 −13 −4 −5 8558 −8 −3 −4 9574 1 −2 −3 10863 14 −1 −2 12526 11 0 −1 14824 37 −10 −9 18138 −5 −9 −8 23334 −9 −8 −7 32695 −31 −7 −6 54756 16 9R (10) QR (10, 4) −7 −8 36357 −27 −6 −7 39404 −13 −5 −6 42994 −8 −4 −5 47349 45 −3 −4 52603 40 −2 −3 59098 −39 9R (14) QR (9, 8) 5 6 12451 −22 4 5 13784 −2 3 4 15396 −11 2 3 17445 −15 1 2 20142 −4 0 1 23825 18 10 9 29090 −3 9 8 37439 44 8 7 52296 −23 9R (18) QR (10, 7) −9 −10 27986 −123 −8 −9 30092 −27 −7 −8 32480 43 −6 −7 35133 −11 −5 −6 38456 113 −4 −5 42164 −18 −3 −4 46943 67 −2 −3 52703 −42 −1 −2 60276 −20 9R (32) QR (12, 6) −9 −10 34648 −7 −8 −9 36958 −4 −7 −8 39597 −2 −6 −7 42645 4 −5 −6 46197 8 −4 −5 50390 5 −3 −4 55418 −2 −2 −3 61573 −4 9R (36) QR (11, 9) −10 −11 49957 3 −9 −10 53185 5 −8 −9 56837 −14 −7 −8 61072 7 9R (38) RP (4, 1) 3 2 53762 9R (40) PP (3, 2) 2 1 41743 −9 1 0 42672 1 0 −1 43328 25 −1 −2 43583 −17 9R (42) RP (4, 2) −3 −2 13498 8 −2 −1 18579 1 −3 −4 21105 4 −1 0 29844 −4 −2 −3 36972 −2 13 C16 O2 10P (40) QP (11, 2) −9 −8 10065 106 −8 −7 10851 126 −7 −6 11593 −25 −6 −5 12598 −75 −5 −4 14134 196 −4 −3 15624 139 −3 −2 17547 129 −2 −1 19899 −4 −1 0 23070 −143 −10 −11 27707 −250 −9 −10 34619 −341 −8 −9 46951 301 10P (26) QP (11, 9) −10 −9 44267 −6 −9 −8 47446 13 −8 −7 51062 −15 −7 −6 55343 12 −6 −5 60352 −4 10P (22) QP (11, 10) −5 −4 11087 −45 −4 −3 12324 −44 −3 −2 13915 4 −2 −1 15929 34 −1 0 18554 15 −10 −11 22376 −2 −9 −10 28025 24 −8 −9 37391 −15 −7 −8 56350 2 10P (16) QP (10,8) 9 8 26032 −19 8 7 28130 −2 7 6 30586 13 6 5 33461 −16 5 4 37042 50 4 3 41319 −11 3 2 46793 −29 2 1 54005 11 10P (12) QP (10,9) −9 −8 20357 −36 −8 −7 22043 15 −7 −6 23966 17 −6 −5 26251 15 −5 −4 29025 17 −4 −3 32459 25 −3 −2 36780 1 −2 −1 42449 −18 −1 0 50176 −65 0 1 61541 38 10P (8) QP (9, 6) −8 −7 30126 −3 −7 −6 32860 −8 −6 −5 36154 1 −5 −4 40177 7 −4 −3 45197 6 −3 −2 51647 0 −2 −1 60254 −3 10R (12) QP (7, 1) −6 −5 27220 44 −5 −4 30509 −41 −4 −3 34891 12 −3 −2 40601 −36 −2 −1 48692 29 −1 0 60622 −5 10R (16) QP (7, 4) −6 −5 33129 −5 −5 −4 37282 0 −4 −3 42625 9 −3 −2 49728 −3 −2 −1 59701 −1 10R (28) QP (6, 1) −5 −4 4095 15 −4 −3 4708 2 −3 −2 5521 −37 −2 −1 6738 −48 −1 0 8781 70 −5 −6 12320 −51 −4 −5 20718 24 9P (32) QQ (10, 9) M − 1M 29957a 9P (28) QQ (11, 11) M + 1M 34118a 9P (16) PP (11, 9) 10 9 47831 −104 9 8 50216 61 8 7 52676 85 7 6 55286 9 6 5 58200 −52 9R (8) QR (3, 1) −2 −3 56817 9R (10) QR (3, 3) −2 −3 56556 9R (16) PP (8, 8) −7 −6 22940 −11 −6 −5 24626 −25 −5 −4 26632 9 −4 −3 28948 9 −3 −2 31702 6 −2 −1 35039 6 −1 0 39152 −5 0 1 44395 16 1 2 51205 −6 2 3 60524 −4 9R (20) PP (10, 2) 9 10 24203 5 8 9 25595 −17 7 8 27192 −11 6 7 29068 61 5 6 31044 −25 4 5 33421 −30 3 4 36251 15 2 3 39536 2 12 C18 O2 10P (28) QP (5, 2) −4 −3 9666 37 −3 −2 11576 22 −2 −1 14480 40 −1 0 19242 −6 0 1 28916 60 −4 −5 28916 1 1 2 57547 −34 −3 −4 57800 −15 10R (10) QP (2, 1) 1 0 3155 −10 0 −1 9440 2 1 2 9482 1 10R (16) QQ (11, 6) M + 1M 29223a 10R (18) QQ (12, 8) M + 1M 11572a 10R (22) QQ (13, 10) M − 1M 40940a 10R (26) QQ (10, 7) M + 1M 8719a 9P (44) PP (7, 5) 5 4 3478 −4 4 3 3686 −3 3 2 3921 −2 2 1 4188 −1 1 0 4496 2 0 −1 4847 1 −1 −2 5258 1 −2 −3 5744 0 −3 −4 6334 2 −4 −5 7058 5 −5 −6 7959 0 −6 −7 9127 −4 9P (34) RP (9, 5) −8 −7 43006 4 −7 −6 47769 −6 −6 −5 53740 2 9P (18) RP (7, 4) 6 5 21985 2 5 4 25366 2 4 3 29969 −2 6 7 36601 −3 5 6 47037 2 9P (14) PP (5, 2) 4 5 44883 1 3 4 50520 −2 2 3 57819 1 9P (8) RP (6, 4) 5 4 4285 −1 4 3 5122 30 3 2 6170 −101 5 6 7339 −6 4 5 10096 17 1 0 11871 42 3 4 16032 −17 2 3 39218 4 9R (10) RP (4, 2) −3 −2 12456 −3 −2 −1 17157 0 −3 −4 19496 11 −1 0 27560 −1 −2 −3 34125 −4 9R (20) RP (3, 1) 2 1 32911 −3 2 3 46200 1 1 0 57116 1 9R (22) PP (2, 2) 1 0 55173 9R (34) PQ (7, 7) −6 −7 49148 1 −5 −6 53134 −2 −4 −5 57831 1 N2 O P (30) QP (9, 8)−8 −7 14797 −82 −7 −6 16208 −24 −6 −5 17869 14 −5 −4 19859 21 −4 −3 22321 4 −3 −2 25478 −28 −2 −1 29769 13 −1 0 35742 33 −8 −9 44741 −37 −7 −8 59820 28 R (21) QP (4, 3)−3 −2 27105 −5 −2 −1 34912 6 −1 0 49016 −2 R (32) QP (3, 1)2 1 45736 R (33) QP (3, 2)−2 −1 564 −4 −1 0 844 −7 0 1 1708 6 −2 −3 1708 4
a Lamb dips with various
M ’s overlap at one resonant field.
Table 2
Observed Stark Resonances in PH3 for A Levels with Large A 1 A 2 Splittings
Assignmenta E obs (V/cm)ν 1 − ν c b (MHz)
M ′M ″12 C16 O2 10P (18) QP (5, 3) −4 −3 10135 878.2 −3 −2 12165 878.4 −2 −1 15207 878.3 −1 0 20259 878.2 −1 −0 20304 878.4 −0 1 30390 878.3 −4 −5 30408 877.8 0 1 30507 878.3 −3 −4 60978 877.3 1 2 61142 878.3 9P (24) RP (11, 3) 10 11 20019 −2970.8 9 10 21593 −2975.5 8 9 23784 −2971.9 7 8 26347 −2971.0 6 7 29489 −2971.7 5 6 33593 −2971.6 4 5 39143 −2971.3 3 4 47072 −2971.8 2 3 59724 −2971.0 9P (20) PP (8, 3) −7 8 25608 4955.6 −6 7 29501 4955.6 −5 6 34784 4955.3 −4 5 42376 4955.5 −3 4 54184 4954.8 9P (10) RP (9, 3) 8 −9 5329 −2516.8 7 −8 6020 −2516.4 6 −7 6902 −2514.6 5 −6 8132 −2515.7 4 −5 9886 −2516.8 3 −4 12574 −2517.3 2 −3 17168 −2515.2 1 −2 27156 −2517.2 0 −1 58496 −2515.2 9R (10) UP (6, 0) 5 6 30653 −5877.6 4 5 38316 −5879.0 3 4 51062 −5879.4 9R (22) UP (5, 0) −4 5 10938 2536.1 −3 4 14595 2537.4 −2 3 21889 2534.9 −1 2 43991 2536.2 9R (30) RP (5, 3) −4 −3 21090 3056.0 −3 −2 26364 3054.2 −4 −5 35154 3058.9 −3 −4 52914 3062.9 13 C16 O2 10R (14) QP (7, 3) 6 5 17467 −811.7 5 4 19658 −811.9 4 3 22494 −812.9 3 2 26208 −811.8 2 1 31451 −811.8 1 −0 38991 −811.6 1 0 39613 −811.4 0 −1 51263 −811.7 6 7 52336 −811.3 −0 −1 53611 −811.6 9P (14) PP (13, 3) 12 −13 15392 −6707.7 11 −12 16694 −6708.0 10 −11 18221 −6707.5 9 −10 20070 −6707.7 8 −9 22330 −6707.6 7 −8 25163 −6707.5 6 −7 28822 −6707.5 5 −6 33718 −6707.2 4 −5 40727 −6709.7 3 −4 51127 −6708.1 12 C18 O2 9P (46) PP (8, 3) −7 8 34305 6358.4 −6 7 39528 6357.3 −5 6 46641 6357.6 −4 5 56853 6356.2 9P (36) RP (9, 3) −3 −4 36611 1149.1 −2 −3 39151 1149.0 −1 −2 48453 1149.0 9P (34) UP (8, 0) 7 8 51808 −7299.8 6 7 60428 −7298.5 9P (32) QR (8, 3) −9 8 1730 387.1 −8 7 1956 385.8 −6 7 2163 386.6 −5 6 2536 385.7 −1 2 8554 387.2 −2 1 10503 385.7 7 8 13820 385.9 6 7 15097 385.5 −0 1 18721 386.7 1 2 29743 387.9 −1 0 35163 389.1 −1 −0 38419 389.1 9 8 40694 388.9 0 1 45462 386.7 −2 −1 52016 388.0 8 7 54224 389.2 9P (28) RP (8, 3) −7 8 8969 2602.8 −6 7 10356 2602.4 −5 6 12248 2601.9 −4 5 14993 2601.9 −3 4 19320 2602.0 −2 3 27150 2603.0 −1 2 45402 2603.7 −7 −8 59188 2603.7 −6 −5 41682 2596.0 −5 −4 48046 2601.3 −4 −3 56520 2601.9 9P (16) UP (6, 0) 5 6 4006 −819.4 4 5 5000 −818.5 3 4 6671 −819.0 2 3 10003 −818.9 1 2 20007 −819.9 9P (10) QR (11, 3) −12 11 42047 5916.4 −11 10 46082 5917.9 −10 9 50972 5919.5 −9 8 56994 5918.4 9P (6) UP (5, 0) 4 5 35589 −8257.3 3 4 47413 −8257.6 9R (12) QR (14, 3) −6 −5 10814 1576.9 −5 −4 13688 1577.0 −2 −3 16294 1577.2 −4 −3 18774 1576.7 −1 −2 24191 1576.7 −3 −2 29907 1576.6 9R (32) RP (2, 0) −1 −2 28445 6681.5 −1 0 28718 6681.6
a The quantum number
M is negative for the upper component and is positive for the lower component of an
A 1 A 2 doublet.
b ν l is a laser frequency, and
ν c is a separation (in megahertz) between centers of
A 1 A 2 doublets in the excited and ground vibrational states.
Table 3
The ν 2 Band of PH3 and Effective Dipole Moment in the ν 2 State (A 1 A 2 Doublet Lines Are Excluded)
Transition Laser ν m − ν l (MHz)ν m (cm−1 )μ ′(D)QP (11.2)13 CO2 10P (40)−122.0(1.5) 878.429 52(25) 0.57397(57) QP (11.9)13 CO2 10P (26)−2608.(11) 891.486 95(40) 0.57345(69) QP (11.10)13 CO2 10P (22)−486.5(1.1) 895.134 34(25) 0.57362(8) QP (10.8)13 CO2 10P (16)1638.8(4.1) 900.423 31(30) 0.57360(53) QP (10.9)13 CO2 10P (12)−1451.2(1.7) 903.701 33(25) 0.57447(33) QP (9.6)13 CO2 10P (8)−1738.5(0.9) 906.994 85(25) 0.57372(12) QP (9.8)N2 O P (30) −1144.7(2.0) 912.321 10(25) 0.57367(12) QP (7.1)13 CO2 10R (12)−418.2(1.2) 923.097 38(25) 0.57361(89) QP (7.4)13 CO2 10P (16)−2053.2(1.7) 925.855 42(25) 0.57426(23) QP (6.1)13 CO2 10R (28)−83.8(0.9) 933.877 90(25) 0.57282(76) QP (6.4)CO2 10P (28) −2211.6(3.8) 936.729 98(30) 0.57438(61) QP (5.2)C18 O2 10P (28) −556.1(0.6) 944.978 18(25) 0.57400(11) QP (4.3)CO2 10P (6) 1315.9(0.7) 956.228 88(25) 0.57403(10) QP (4.3)N2 O R (21) −3524.6(5.4) 956.229 00(30) 0.57404(69) QP (3.1)N2 O R (32) 3340.8 964.572 65(40) (0.57398)a QP (3.2)N2 O R (33) −81.9(0.8) 965.174 88(25) 0.5737(23) QQ (15.8)CO2 10R (8) 471.2 967.722 95(30) 0.57394b QP (2.1)C18 O2 10R (10) 457.6(1.2) 974.175 57(25) 0.57396(74) QQ (11.6)C18 O2 10R (16) 383.8 977.763 11(30) 0.57393b QQ (12.8)C18 O2 10R (18) 171.5 978.899 08(30) 0.57395b QQ (13.10)C18 O2 10R (22) −649.9 981.076 98(30) 0.57395b QQ (9.5)CO2 10R (30) −724.1 982.071 38(30) 0.57400b QQ (10.7)C18 O2 10R (26) 160.3 983.201 10(30) 0.57395b QQ (8.4)CO2 10R (32) −159.7 983.246 92(30) 0.57397b QQ (14.12)CO2 10R (34) −35.1 984.382 05(30) 0.57395b QQ (11.9)CO2 10R (36) −1064.6 985.452 80(30) 0.57395b QQ (10.9)13 CO2 9P (32)−708.2 989.049 19(30) 0.57394b QQ (11.11)13 CO2 9P (28)822.2 993.070 02(30) 0.57397b QR (3.1)13 CO2 9R (8)2432.2 1024.448 87(30) (0.57396)a QR (3.3)13 CO2 9R (10)7348.5 1026.023 39(45) (0.57396)a QR (5.4)CO2 9P (26) 3543.8(7.1) 1041.397 28(30) (0.57395)a QR (5.5)CO2 9P (24) −445.0(0.2) 1043.148 40(25) 0.57407(10) QR (7.7)CO2 9P (4) −4110.(11) 1060.433 57(45) 0.57409(82) QR (8.8)CO2 9R (6) 3395.(14) 1069.127 34(50) 0.5738(11) QR (9.7)CO2 9R (10) 332.3(0.5) 1071.894 85(25) 0.57418(5) QR (10.4)CO2 9R (10) 828.6(2.8) 1071.911 41(25) 0.57377(97) QR (9.8)CO2 9R (14) −611.7(0.9) 1074.626 09(25) 0.57391(7) QR (10.7)CO2 9R (18) 1293.1(4.7) 1077.345 65(30) 0.5738(11) QR (12.6)CO2 9R (32) 873.5(0.3) 1085.794 58(25) 0.57509(9) QR (11.9)CO2 9R (36) 2499.(11) 1088.031 66(45) 0.57393(84)
a Dipole moment calculated by
Eq. (15) used to analyze this transition.
b Uncertainty is not given because only one resonant field is observed.
Table 4
The ν 4 Band of PH3 and Effective Dipole Moment in the ν 4 State (A 1 A 2 Doublet Lines Are Excluded)
Transition Laser ν m − ν l (MHz)ν m (cm−1 )M ′ (D)PP (13.13)CO2 10R (14) 1339.9(1.6) 971.974 95(25) 0.57758(19) PP (13.11)CO2 10R (30) 554.9(0.3) 982.114 04(25) 0.57846(5) PP (12.11)CO2 10R (42) 902.4(1.1) 988.676 73(25) 0.57751(24) PP (11.9)13 CO2 9P (16)1695.(29) 1004.336 41(100) 0.5808(19) PP (8.8)13 CO2 9R (16)−1424.0(0.4) 1029.787 63(25) 0.57812(6) PP (10.2)13 CO2 9R (20)−254.7(0.8) 1032.386 01(25) 0.83338(89) PP (7.7)CO2 9P (26) 1158.2(0.7) 1041.317 71(25) 0.57826(9) RP (11.7)CO2 9P (22) 1228.9(0.6) 1045.062 66(25) 0.57436(8) RP (10.2)CO2 9P (18) −168.2(0.5) 1048.655 20(25) 0.47720(53) PP (7.5)C18 O2 9P (44) 125.0(0.1) 1048.710 58(25) 0.58019(4) PP (7.5)CO2 9P (18) 1493.2(0.2) 1048.710 62(25) 0.58005(3) RP (9.5)CO2 9P (8) 1420.3(0.8) 1057.347 54(25) 0.57155(10) RP (9.5)C18 O2 9P (34) −3420.(27) 1057.347 85(95) 0.5718(19) PP (7.1)CO2 9P (6) 113.4(0.2) 1058.952 50(25) – RP (7.4)CO2 9R (8) 3611.4(1.8) 1070.582 77(25) 0.57450(11) RP (7.4)C18 O2 9P (18) 2273.5(0.9) 1070.582 89(25) 0.57455(7) PP (5.2)C18 O2 9P (14) −1586.0(0.6) 1073.525 96(25) 0.60436(17) RP (6.4)C18 O2 9P (8) 566.4(8.0) 1078.061 31(60) 0.5774(10) RP (4.1)CO2 9R (38) 5980. 1089.200 59(45) (0.55578)a PP (3.2)CO2 9R (40) 2070.2(1.5) 1090.097 42(25) 0.57934(34) RP (4.2)CO2 9R (42) −2160.4(1.6) 1090.958 13(25) 0.57752(22) RP (4.2)C18 O2 9R (10) −1996.0(2.0) 1090.958 08(25) 0.57765(29) RP (3.1)C18 O2 9R (20) 5560.5(2.9) 1097.336 08(25) 0.57413(24) PP (2.2)C18 O2 9R (22) 8067.5 1098.586 49(60) (0.57904)a PQ (7.7)C18 O2 9R (34) 3222.3(2.3) 1105.019 30(25) 0.57871(16)
a Dipole moment calculated by
Eq. (15) used to analyze this transition.
Table 5
A 1 A 2 Doublet Transitions in the ν 2 and ν 4 Bands and A 1 A 2 Splittings in the ν 2 and ν 4 States of PH3
A 2 − A 1 (MHz)
Transition ν (cm−1 )J K l Obs. Calc.a QP (5.3)A 2 –A 1 945.950 96(25) 4 3 3.4 ± 0.5 2.5 A 1 –A 2 945.950 91(25) QP (7.3)A 2 –A 1 924.555 02(25) 6 3 36.3 ± 1.0 26.2 A 1 –A 2 924.554 24(25) QR (8.3)A 2 –A 1 1059.140 27(25) 9 3 −321.7 ± 1.0 −227.6 A 1 –A 2 1059.150 06(25) QR (11.3)A –A b 1076.376 46(90) 12 3 (1300)c 972.0 QR (14.3)A 1 –A 2 1092.290 43(30) 15 3 −4000 ± 250 −2898.6 RP (2.0)A 2 –A 1 1103.813 14(30) 1 1 1 10 498.9d 10 541.4 UP (5.0)A –A b 1079.767 66(30) 4 4 1 (200)c 170.2 RP (5.3)A –A b 1084.533 21(30) 4 4 1 (200)c UP (6.0)A –A b 1072.079 86(40) 5 4 1 −580 ± 140 −547.4 PP (8.3)A 2 –A 1 1046.739 49(60) 7 2 −1 3000 ± 150 2852.8 UP (8.0)A –A 1 b 1057.705 41(30) 7 4 1 (−2426)° −2286.6 RP (8.3)A 1 –A 2 1062.447 82(50) 7 4 1 −2426 ± 20 RP (9.3)A 2 –A 1 1055.773 12(25) 8 4 1 3901 ± 10 3712.4 A 1 –A 2 1055.644 89(25) RP (11.3)A 1 –A 2 1043.132 16(30) 10 4 1 7990 ± 100 7646.0 PP (13.3)A 2 –A 1 1006.080 14(30) 12 2 −1 −11 320 ±1400 −11 477.8
a Calculated with the constants in Ref.
3 .
b Frequency between the centers of
A 1 A 2 doublets in the upper state and the lower state.
c Assumed
A 1 A 2 splitting used to calculate
ν l −
ν c in
Table 2 .
d Observed by microwaves spectroscopy.
20 This value was used to analyze this transition.
Table 6
Effective Dipole Moments (D) in the of ν 2 and ν 4 States PH3
J K l μ obs. μ calc. μ o − μ c (μ o − μ c )a v 2 = 11 1 0.5740(7) 0.5740 0.0000 (−0.0002) 2 1 0.5740 2 2 0.5737(23)b 0.5740 −0.0003 (−0.0004) 3 3 0.5740(1) 0.5740 0.0001 (−0.0001) 4 1 0.5740 (0.0000) 4 2 0.5740(1) 0.5740 0.0000 (0.0000) 4 3 0.5740(1) 0.5740 0.0000 (−0.0001) 5 1 0.5728(8)b 0.5740 −0.0011 (−0.0012) 5 4 0.5744(6) 0.5740 0.0004 (0.0003) 6 1 0.5736(9) 0.5740 −0.0003 (−0.0003) 6 3 0.5740 6 4 0.5743(2) 0.5740 0.0003 (0.0003) 6 5 0.5741(1) 0.5740 0.0001 (0.0001) 8 4 0.5740 0.5739 0.0000 (0.0001) 8 6 0.5737(1) 0.5739 −0.0002 (−0.0002) 8 7 0.5741(8) 0.5739 0.0002 (0.0001) 8 8 0.5737(1) 0.5739 −0.0003 (−0.0004) 9 3 0.5738 9 5 0.5740 0.5739 0.0001 (0.0002) 9 8 0.5736(5) 0.5739 −0.0003 (−0.0003) 9 9 0.5745(3) 0.5739 0.0005 (0.0005) 10 2 0.5740(6) 0.5739 0.0000 (0.0003) 10 7 0.5742(1) 0.5739 0.0002 (0.0004) 10 8 0.5739(1) 0.5739 0.0000 (0.0001) 10 9 0.5735(7) 0.5739 −0.0005 (−0.0005) 10 10 0.5736(1) 0.5739 −0.0003 (−0.0004) 11 4 0.5738(10)b 0.5739 −0.0002 (0.0001) 11 6 0.5739b 0.5740 0.0000 (0.0002) 11 7 0.5738(H)b 0.5740 −0.0002 (0.0000) 11 9 0.5740b 0.5739 0.0000 (0.0001) 11 11 0.5740b 0.5739 0.0001 (0.0000) 12 3 0.5739 12 8 0.5740b 0.5740 0.0000 (0.0002) 12 9 0.5739(8)b 0.5739 0.0000 (0.0002) 13 6 0.5751(1)b 0.5740 0.0011 (0.0015) 13 10 0.5740b 0.5740 0.0000 (0.0002) 14 12 0.5740b 0.5739 0.0000 (0.0002) 15 3 0.5737 15 8 0.5739b 0.5740 −0.0001 (0.0003) v 4 = 11 1 1 0.5788 2 11 −1 0.5793(3) 0.5795 −0.0001 (0.0001) 2 2 1 0.5741(2) 0.5738 0.0003 (0.0022) 3 3 1 0.5775(2) 0.5764 0.0012 (0.0031) 4 1 −1 0.6044(2) 0.6047 −0.0004 (−0.0038) 4 4 1 0.5754 5 4 1 0.5703 5 5 1 0.5774(10)b 0.5775 0.0001 (0.0020) 6 4 −1 0.5801(1) 0.5806 −0.0005 (−0.0007) 6 5 1 0.5746(1) 0.5740 0.0005 (0.0030) 6 6 −1 0.5783(1) 0.5790 −0.0008 (0.0006) 7 2 1 0.6166 7 4 1 0.5519 7 6 −1 0.5787(2) 0.5793 −0.0006 (0.0001) 7 7 −1 0.5781(1) 0.5790 −0.0009 (0.0005) 8 4 1 0.5399 8 6 1 0.5716(1) 0.5711 0.0005 (0.0035) 9 1 −1 0.8334(9) 0.8330 0.0004 (−0.0103) 9 3 1 0.4772(5) 0.4776 −0.0004 (0.0042) 10 4 1 0.5156 10 8 −1 0.5808(19)b 0.5799 0.0009 (0.0009) 10 8 1 0.5744(1) 0.5738 0.0006 (0.0035) 11 10 −1 0.5775(2)b 0.5792 −0.0017 (−0.0011) 12 2 −1 0.7147 12 10 −1 0.5785(1)b 0.5797 −0.0012 (−0.0013) 12 12 −1 0.5776(2)b 0.5790 −0.0014 (0.0000)
a The values for
μ o −
μ c in parentheses are for the least-squares analysis with two parameters,
μ 2 and
μ 4 .
b This value is removed from the least-squares analysis.
Table 7
Dipole Moments in the ν 2 and ν 4 States of PH3 (D)a
μ 2 μ 4 μ t 0.57420(27) 0.57904(32) −0.01100(92)
a The errors quoted are 2.5 times the standard deviation.