pyrazole: reproducing the fit in Table 6 of JPCA 119,1731(2015) ! ! Starting geometry = MP2/cc-pVDZ (but any other reasonable starting point is ! just as good. ! ! Experimental rotational constants from L.Nyygard et al., J.Mol.Struct. 22,401(1974) ! ! Be-B0 values = B3LYP/6-311+G(3df,2pd) from Table 4 of supplementary information ! for A.G.Csaszar, J,Demaison, H.D.Rudolph, J.Phys.Chem.A 119,1731(2015) ! ! g-factors are back-calculated from the same SI table as above. ! 9 1 0 0 0 0.0000000 0.0000000 0.0000000 14.0030744 2 1 0 0 1.3437700 0.0000000 0.0000000 14.0030744 3 2 1 0 1.3527700 103.5980000 0.0000000 12.0000000 4 3 2 1 1.4156900 112.0490000 0.0000000 12.0000000 5 1 2 3 1.3652600 114.2170000 0.0000000 12.0000000 6 1 2 3 1.0144100 118.6340000 180.0000000 1.0078250 7 3 2 1 1.0897900 119.1190000 180.0000000 1.0078250 8 4 3 2 1.0885000 128.4210000 180.0000000 1.0078250 9 5 1 2 1.0889000 121.8410000 180.0000000 1.0078250 ! ! Parent 1-D 3-D 4-D 5-D 1-15N 2-15N 3_13C 4-13C 5-13C ! 1 2 3 4 5 6 7 8 9 10 ! A ± dA 9618.770 9455.230 9435.783 9566.176 9537.304 9488.641 9618.304 9457.566 9582.358 9571.674 ! B± dB 9412.535 8859.733 8774.190 8617.847 8677.868 9339.851 9180.010 9340.094 9193.394 9223.004 ! C ± dC 4755.853 4572.847 4545.189 4532.324 4542.381 4705.424 4695.610 4697.835 4690.511 4695.634 ! ! column: 32 38 51 72 91 ! | | | | | ! --++--++++++++++++++ cccccccccccccccccccc ! ! Csaszar et al values ! placed here for comparison NO OF PARAMETERS TO BE FITTED: 17 atom no., parameter no. 6 1 0 N1-H 1.0014 atom no., parameter no. 2 1 0 N1-N2 1.3431 atom no., parameter no. 3 1 0 N2=C3 1.3286 atom no., parameter no. 5 1 0 N1-C5 1.3523 atom no., parameter no. 4 1 0 1.47 <- improves conv. C3-C4 1.4093 atom no., parameter no. 7 1 0 C3-H 1.0755 atom no., parameter no. 8 1 0 C4-H 1.0736 atom no., parameter no. 9 1 0 C5-H 1.0740 atom no., parameter no. 3 2 0 N1-N2-C3 104.18 atom no., parameter no. 4 2 0 N1-C3-C4 111.90 atom no., parameter no. 5 2 0 N2-N1-C5 113.24 atom no., parameter no. 6 2 0 H-N1-N2 118.97 atom no., parameter no. 7 2 0 N2-C3-H 119.49 atom no., parameter no. 8 2 0 C3-C4-H 128.32 atom no., parameter no. 9 2 0 N1-C5-H 121.84 atom no., parameter no. FIX 4 3 0 atom no., parameter no. FIX 5 3 0 ! ! column: 32 36 50 64 78 ! | | | | | ! ++--++++++++++++++--------------++++++++++++++ ! ! expt. B0 g_bb calc Be-B0 NO OF CONSTANTS TO BE FITTED: 30 constant,species,value 1 1 9618.770 -0.0788 78.418 parent constant,species,value 2 1 9412.535 -0.1317 79.703 constant,species,value 3 1 4755.853 0.0632 41.431 constant,species,value 1 2 9455.230 -0.1253 81.054 1-D constant,species,value 2 2 8859.733 -0.0798 65.764 constant,species,value 3 2 4572.847 0.0609 37.997 constant,species,value 1 3 9435.783 -0.1197 77.298 3-D constant,species,value 2 3 8774.190 -0.0834 70.934 constant,species,value 3 3 4545.189 0.0609 38.714 constant,species,value 1 4 9566.176 -0.0972 81.474 4-D constant,species,value 2 4 8617.847 -0.1055 66.561 constant,species,value 3 4 4532.324 0.0603 38.448 constant,species,value 1 5 9537.304 -0.0913 75.831 5-D constant,species,value 2 5 8677.868 -0.1110 71.890 constant,species,value 3 5 4542.381 0.0601 38.618 constant,species,value 1 6 9488.641 -0.1063 81.197 1-15N constant,species,value 2 6 9339.851 -0.1039 75.122 constant,species,value 3 6 4705.424 0.0627 40.925 constant,species,value 1 7 9618.304 -0.0784 77.791 2-15N constant,species,value 2 7 9180.010 -0.1285 77.420 constant,species,value 3 7 4695.610 0.0628 40.683 constant,species,value 1 8 9457.566 -0.1023 75.230 3-13C constant,species,value 2 8 9340.094 -0.1072 79.869 9340.099 in JCP2015 constant,species,value 3 8 4697.835 0.0628 40.662 9340.094 Nyygard constant,species,value 1 9 9582.358 -0.0895 80.055 4-13C constant,species,value 2 9 9193.394 -0.1189 75.078 constant,species,value 3 9 4690.511 0.0625 40.617 constant,species,value 110 9571.674 -0.0816 75.824 5-13C constant,species,value 210 9223.004 -0.1263 79.168 constant,species,value 310 4695.634 0.0624 40.657 ! ! species 2 = 1-D ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 6 4 2.0141017778 ! ! species 3 = 3-D ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 7 4 2.0141017778 ! ! species 4 = 4-D ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 8 4 2.0141017778 ! ! species 5 = 5-D ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 9 4 2.0141017778 ! ! species 6 = 1-15N ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 1 4 15.0001088982 ! ! species 7 = 2-15N ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 2 4 15.0001088982 ! ! species 8 = 3-13C ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 3 4 13.0033548378 ! ! species 9 = 4-13C ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 4 4 13.0033548378 ! ! species 10 = 5-13C ! NO OF CHANGES FROM PARENT SP.: 1 atom no.,parameter no.,value 5 4 13.0033548378 ! !-------------------------------------------------------------------------------