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Anthony Scemama 2020-08-03 17:39:05 +02:00
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@ -2073,82 +2073,86 @@ return result
**** CIPSI
***** Table
#+NAME: dz-cipsi-inf
| | e_cal | ae_cal | ae_nr | ae_diff | Ndet |
| | Hartree | Hartree | Hartree | kcal/mol | |
|---------+------------+----------+----------+------------+----------|
| Be | -1.000525 | | | | 21 |
| C | -5.409601 | | | | 267 |
| Cl | -14.874670 | | | | 10252 |
| F | -24.092712 | | | | 4775 |
| H | -0.499045 | | | | 1 |
| Li | -0.195611 | | | | 1 |
| N | -9.760494 | | | | 538 |
| Na | -0.174227 | | | | 1 |
| O | -15.830021 | | | | 2191 |
| P | -6.442091 | | | | 940 |
| S | -10.064312 | | | | 5694 |
| Si | -3.747834 | | | | 467 |
|---------+------------+----------+----------+------------+----------|
| BeH | -1.553678 | 0.054107 | 0.079400 | -15.871334 | 224 |
| C2H2 | -12.406308 | 0.589016 | 0.642400 | -33.499063 | 6379033 |
| C2H4 | -13.654291 | 0.838909 | 0.899000 | -37.707779 | 10591776 |
| C2H6 | -14.883776 | 1.070303 | 1.136900 | -41.790396 | 17334909 |
| CH | -6.030933 | 0.122287 | 0.133900 | -7.287361 | 4424 |
| CH2_1A1 | -6.674392 | 0.266701 | 0.288900 | -13.929894 | 33542 |
| CH2_3B1 | -6.693524 | 0.285832 | 0.304100 | -11.463058 | 30834 |
| CH3 | -7.368561 | 0.461825 | 0.490800 | -18.182134 | 166447 |
| CH3Cl | -22.365873 | 0.584466 | 0.631000 | -29.200268 | 15590288 |
| CH4 | -8.040301 | 0.634519 | 0.670300 | -22.452979 | 3122549 |
| CN | -15.420599 | 0.250505 | 0.288800 | -24.030615 | 4176099 |
| CO | -21.620625 | 0.381003 | 0.413700 | -20.517751 | 3213703 |
| CO2 | -37.628565 | 0.558923 | 0.621400 | -39.205250 | 14178168 |
| CS | -15.715849 | 0.241936 | 0.274000 | -20.120211 | 4718077 |
| Cl2 | -29.813061 | 0.063720 | 0.094000 | -19.001066 | 12989304 |
| ClF | -39.034108 | 0.066725 | 0.100100 | -20.942989 | 12655275 |
| ClO | -30.770645 | 0.065953 | 0.104700 | -24.314036 | 10324859 |
| F2 | -48.220427 | 0.035004 | 0.062200 | -17.066000 | 8302442 |
| H2CO | -22.787839 | 0.550127 | 0.596700 | -29.224860 | 10264703 |
| H2O | -17.164684 | 0.336572 | 0.371900 | -22.168529 | 99885 |
| H2O2 | -33.028553 | 0.370420 | 0.429400 | -37.010345 | 10320031 |
| H2S | -11.328300 | 0.265898 | 0.292000 | -16.379580 | 259286 |
| H3COH | -23.991137 | 0.755334 | 0.818700 | -39.762604 | 16358119 |
| H3CSH | -18.167888 | 0.697794 | 0.757000 | -37.152112 | 18413076 |
| HCN | -16.117008 | 0.447868 | 0.496900 | -30.767913 | 8167342 |
| HCO | -22.143105 | 0.404438 | 0.444700 | -25.264958 | 12334847 |
| HCl | -15.530706 | 0.156990 | 0.171000 | -8.791277 | 152328 |
| HF | -24.794333 | 0.202576 | 0.226100 | -14.761344 | 49030 |
| HOCl | -31.423955 | 0.220218 | 0.264700 | -27.912624 | 10067128 |
| Li2 | -0.429030 | 0.037807 | 0.038900 | -0.685881 | 10 |
| LiF | -24.483186 | 0.194863 | 0.222000 | -17.028990 | 51591 |
| LiH | -0.779466 | 0.084809 | 0.092430 | -4.782273 | 22 |
| N2 | -19.835410 | 0.314422 | 0.364600 | -31.487034 | 2993655 |
| N2H4 | -22.128697 | 0.611528 | 0.699600 | -55.265985 | 13236879 |
| NH | -10.374955 | 0.115416 | 0.133500 | -11.347816 | 11288 |
| NH2 | -11.017005 | 0.258421 | 0.290400 | -20.067280 | 128829 |
| NH3 | -11.686446 | 0.428816 | 0.475500 | -29.294652 | 913595 |
| NO | -25.793891 | 0.203376 | 0.244500 | -25.805458 | 10184650 |
| Na2 | -0.381541 | 0.033087 | 0.026800 | 3.945450 | 10 |
| NaCl | -15.184843 | 0.135946 | 0.157400 | -13.462618 | 102321 |
| O2 | -31.816781 | 0.156739 | 0.192400 | -22.377521 | 10258769 |
| OH | -16.481147 | 0.152081 | 0.170200 | -11.369835 | 31287 |
| P2 | -13.023492 | 0.139309 | 0.186000 | -29.298875 | 6057350 |
| PH2 | -7.657879 | 0.217697 | 0.244000 | -16.505552 | 199003 |
| PH3 | -8.286026 | 0.346799 | 0.389000 | -26.481581 | 830507 |
| S2 | -20.256329 | 0.127706 | 0.164000 | -22.775099 | 10271330 |
| SO | -26.048230 | 0.153898 | 0.200700 | -29.368798 | 10836590 |
| SO2 | -42.028164 | 0.303811 | 0.414400 | -69.395986 | 10425047 |
| Si2 | -7.591404 | 0.095736 | 0.121000 | -15.853532 | 2113836 |
| Si2H6 | -11.270753 | 0.780813 | 0.849000 | -42.788313 | 13174386 |
| SiH2_1A1 | -4.968424 | 0.222500 | 0.243000 | -12.864193 | 31953 |
| SiH2_3B1 | -4.938794 | 0.192869 | 0.210000 | -10.749905 | 26570 |
| SiH3 | -5.578071 | 0.333101 | 0.363000 | -18.762185 | 435225 |
| SiH4 | -6.222955 | 0.478939 | 0.515000 | -22.628450 | 2954175 |
| SiO | -19.838076 | 0.260221 | 0.306700 | -29.166345 | 4457124 |
|---------+------------+----------+----------+------------+----------|
| | | 23.62 | -23.48 | 12.81 | |
#+TBLFM: @>$3='(org-sbe "madformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$5..@>>$5) );%0.2f
| | Total E | | Delta E | | Reference | Error | |
| | Hartree | | Hartree | | Hartree | kcal/mol | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | e_cal | ae_cal | ae_nr | ae_diff | Ndet | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| Be | -1.000525 | 0.000000 | 0.000000 | 0.000000 | | | |
| C | -5.409599 | 0.000005 | 0.000000 | 0.000008 | | | |
| Cl | -14.874672 | 0.000003 | 0.000000 | 0.000004 | | | |
| F | -24.092714 | 0.000002 | 0.000000 | 0.000003 | | | |
| H | -0.499045 | 0.000000 | | 0.000000 | | | |
| Li | -0.195611 | 0.000000 | | 0.000000 | | | |
| N | -9.760495 | 0.000004 | 0.000000 | 0.000006 | | | |
| Na | -0.174227 | 0.000000 | | 0.000000 | | | |
| O | -15.830021 | 0.000005 | 0.000000 | 0.000007 | | | |
| P | -6.442099 | 0.000004 | 0.000000 | 0.000006 | | | |
| S | -10.064311 | 0.000002 | 0.000000 | 0.000002 | | | |
| Si | -3.747833 | 0.000004 | 0.000000 | 0.000005 | | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| BeH | -1.553657 | 0.000020 | 0.054087 | 0.000020 | 0.079400 | -15.884299 | 0.012745 |
| C2H2 | -12.406315 | 0.000001 | 0.589027 | 0.000011 | 0.642400 | -33.492129 | 0.006743 |
| C2H4 | -13.654309 | 0.000006 | 0.838930 | 0.000012 | 0.899000 | -37.694551 | 0.007803 |
| C2H6 | -14.883546 | 0.000042 | 1.070077 | 0.000043 | 1.136900 | -41.932051 | 0.027188 |
| CH | -6.030934 | 0.000018 | 0.122290 | 0.000018 | 0.133900 | -7.285247 | 0.011601 |
| CH2_1A1 | -6.674394 | 0.000001 | 0.266704 | 0.000005 | 0.288900 | -13.927911 | 0.003396 |
| CH2_3B1 | -6.693528 | 0.000006 | 0.285839 | 0.000008 | 0.304100 | -11.459136 | 0.005163 |
| CH3 | -7.368566 | 0.000005 | 0.461832 | 0.000007 | 0.490800 | -18.177798 | 0.004427 |
| CH3Cl | -22.365840 | 0.000001 | 0.584434 | 0.000006 | 0.631000 | -29.220712 | 0.003816 |
| CH4 | -8.040305 | 0.000000 | 0.634525 | 0.000005 | 0.670300 | -22.449252 | 0.003365 |
| CN | -15.420598 | 0.000003 | 0.250504 | 0.000007 | 0.288800 | -24.031255 | 0.004544 |
| CO | -21.620628 | 0.000002 | 0.381008 | 0.000008 | 0.413700 | -20.514513 | 0.004735 |
| CO2 | -37.628607 | 0.000059 | 0.558965 | 0.000060 | 0.621400 | -39.178355 | 0.037402 |
| CS | -15.715859 | 0.000007 | 0.241949 | 0.000009 | 0.274000 | -20.112329 | 0.005672 |
| Cl2 | -29.813093 | 0.000027 | 0.063750 | 0.000028 | 0.094000 | -18.982410 | 0.017322 |
| ClF | -39.034069 | 0.000003 | 0.066683 | 0.000005 | 0.100100 | -20.969596 | 0.003000 |
| ClO | -30.770680 | 0.000045 | 0.065986 | 0.000045 | 0.104700 | -24.293159 | 0.028395 |
| F2 | -48.220437 | 0.000013 | 0.035009 | 0.000014 | 0.062200 | -17.062405 | 0.008592 |
| H2CO | -22.787835 | 0.000007 | 0.550124 | 0.000010 | 0.596700 | -29.226623 | 0.006371 |
| H2O | -17.164687 | 0.000002 | 0.336575 | 0.000005 | 0.371900 | -22.166891 | 0.003427 |
| H2O2 | -33.028440 | 0.000005 | 0.370306 | 0.000011 | 0.429400 | -37.081794 | 0.007070 |
| H2S | -11.328294 | 0.000005 | 0.265892 | 0.000005 | 0.292000 | -16.382937 | 0.003348 |
| H3COH | -23.991233 | 0.000031 | 0.755432 | 0.000032 | 0.818700 | -39.701171 | 0.019791 |
| H3CSH | -18.167969 | 0.000012 | 0.697878 | 0.000013 | 0.757000 | -37.099583 | 0.008264 |
| HCN | -16.117018 | 0.000010 | 0.447879 | 0.000012 | 0.496900 | -30.761212 | 0.007333 |
| HCO | -22.143045 | 0.000045 | 0.404380 | 0.000045 | 0.444700 | -25.301260 | 0.028375 |
| HCl | -15.530706 | 0.000002 | 0.156989 | 0.000004 | 0.171000 | -8.791842 | 0.002203 |
| HF | -24.794339 | 0.000004 | 0.202580 | 0.000004 | 0.226100 | -14.759161 | 0.002800 |
| HOCl | -31.423913 | 0.000024 | 0.220175 | 0.000024 | 0.264700 | -27.940178 | 0.015246 |
| Li2 | -0.429044 | 0.000060 | 0.037821 | 0.000060 | 0.038900 | -0.676813 | 0.037575 |
| LiF | -24.483187 | 0.000002 | 0.194861 | 0.000003 | 0.222000 | -17.029906 | 0.001685 |
| LiH | -0.779445 | 0.000017 | 0.084788 | 0.000017 | 0.092430 | -4.795199 | 0.010737 |
| N2 | -19.835407 | 0.000003 | 0.314416 | 0.000009 | 0.364600 | -31.491175 | 0.005555 |
| N2H4 | -22.128406 | 0.000214 | 0.611234 | 0.000214 | 0.699600 | -55.450386 | 0.134476 |
| NH | -10.374951 | 0.000002 | 0.115411 | 0.000005 | 0.133500 | -11.351160 | 0.002996 |
| NH2 | -11.017001 | 0.000005 | 0.258415 | 0.000006 | 0.290400 | -20.070801 | 0.004039 |
| NH3 | -11.686444 | 0.000000 | 0.428812 | 0.000004 | 0.475500 | -29.296879 | 0.002613 |
| NO | -25.793826 | 0.000129 | 0.203309 | 0.000129 | 0.244500 | -25.847639 | 0.080893 |
| Na2 | -0.381534 | 0.000022 | 0.033081 | 0.000022 | 0.026800 | 3.941120 | 0.013579 |
| NaCl | -15.184794 | 0.000001 | 0.135896 | 0.000003 | 0.157400 | -13.493887 | 0.001872 |
| O2 | -31.816772 | 0.000121 | 0.156729 | 0.000121 | 0.192400 | -22.383702 | 0.076130 |
| OH | -16.481149 | 0.000002 | 0.152082 | 0.000005 | 0.170200 | -11.369113 | 0.003281 |
| P2 | -13.023495 | 0.000001 | 0.139297 | 0.000008 | 0.186000 | -29.306650 | 0.005094 |
| PH2 | -7.657876 | 0.000002 | 0.217687 | 0.000004 | 0.244000 | -16.511897 | 0.002734 |
| PH3 | -8.286027 | 0.000000 | 0.346793 | 0.000004 | 0.389000 | -26.485578 | 0.002548 |
| S2 | -20.256068 | 0.000060 | 0.127446 | 0.000060 | 0.164000 | -22.938239 | 0.037658 |
| SO | -26.048352 | 0.000018 | 0.154020 | 0.000018 | 0.200700 | -29.292418 | 0.011468 |
| SO2 | -42.028516 | 0.000227 | 0.304162 | 0.000227 | 0.414400 | -69.175360 | 0.142590 |
| Si2 | -7.591467 | 0.000007 | 0.095801 | 0.000010 | 0.121000 | -15.812907 | 0.006403 |
| Si2H6 | -11.270422 | 0.000246 | 0.780484 | 0.000246 | 0.849000 | -42.994362 | 0.154309 |
| SiH2_1A1 | -4.968425 | 0.000005 | 0.222501 | 0.000006 | 0.243000 | -12.863146 | 0.003838 |
| SiH2_3B1 | -4.938797 | 0.000006 | 0.192874 | 0.000007 | 0.210000 | -10.746899 | 0.004274 |
| SiH3 | -5.578078 | 0.000000 | 0.333109 | 0.000004 | 0.363000 | -18.756914 | 0.002380 |
| SiH4 | -6.222956 | 0.000004 | 0.478942 | 0.000006 | 0.515000 | -22.626643 | 0.003517 |
| SiO | -19.838066 | 0.000008 | 0.260212 | 0.000010 | 0.306700 | -29.171779 | 0.006358 |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | 23.63 | 0.04 | -23.49 | 12.81 | 0.04 | | |
#+TBLFM: @>$2='(org-sbe "madformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$3='(org-sbe "maderrformula" (data @5$8..@>>$8) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$6='(org-sbe "sderrformula" (data @5$7..@>>$7) (data_err @5$8..@>>$8) );%0.2f
***** MAD = 23.62
**** QMC with Jastrow
***** Table
@ -3473,16 +3477,86 @@ plot data u 7:xtic(1) w l notitle, data u :7:8 w err notitle, 1 notitle, -1 noti
**** CIPSI
***** Table
#+NAME: tz-cipsi-inf
| | e_cal | ae_cal | ae_nr | ae_diff | Ndet |
| | Hartree | Hartree | Hartree | kcal/mol | |
|---------+------------+----------+----------+------------+----------|
|---------+------------+----------+----------+------------+----------|
|---------+------------+----------+----------+------------+----------|
| | | | | | |
#+TBLFM: @>$3='(org-sbe "madformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$5..@>>$5) );%0.2f
***** MAD =
| | Total E | | Delta E | | Reference | Error | |
| | Hartree | | Hartree | | Hartree | kcal/mol | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | e_cal | ae_cal | ae_nr | ae_diff | Ndet | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| Be | -1.008492 | 0.000096 | 0.000000 | 0.000136 | | | |
| C | -5.428008 | 0.000013 | 0.000000 | 0.000018 | | | |
| Cl | -14.946282 | 0.000006 | 0.000000 | 0.000008 | | | |
| F | -24.163567 | 0.000015 | 0.000000 | 0.000022 | | | |
| H | -0.499043 | 0.000000 | | 0.000000 | | | |
| Li | -0.196093 | 0.000000 | | 0.000000 | | | |
| N | -9.790978 | 0.000017 | 0.000000 | 0.000024 | | | |
| Na | -0.181799 | 0.000000 | | 0.000000 | | | |
| O | -15.882573 | 0.000003 | 0.000000 | 0.000005 | | | |
| P | -6.469736 | 0.000011 | 0.000000 | 0.000016 | | | |
| S | -10.116024 | 0.000004 | 0.000000 | 0.000005 | | | |
| Si | -3.763624 | 0.000004 | 0.000000 | 0.000006 | | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| BeH | -1.581896 | 0.000006 | 0.074361 | 0.000096 | 0.079400 | -3.161966 | 0.060369 |
| C2H2 | -12.480026 | 0.000012 | 0.625924 | 0.000029 | 0.642400 | -10.338930 | 0.018082 |
| C2H4 | -13.728870 | 0.000006 | 0.876682 | 0.000027 | 0.899000 | -14.004549 | 0.016869 |
| C2H6 | -14.962048 | 0.000071 | 1.111774 | 0.000075 | 1.136900 | -15.766666 | 0.047243 |
| CH | -6.056891 | 0.000012 | 0.129840 | 0.000018 | 0.133900 | -2.547402 | 0.011185 |
| CH2_1A1 | -6.707051 | 0.000001 | 0.280957 | 0.000013 | 0.288900 | -4.984375 | 0.008216 |
| CH2_3B1 | -6.722856 | 0.000001 | 0.296762 | 0.000013 | 0.304100 | -4.604681 | 0.008211 |
| CH3 | -7.405038 | 0.000003 | 0.479901 | 0.000013 | 0.490800 | -6.839150 | 0.008352 |
| CH3Cl | -22.482202 | 0.000192 | 0.610783 | 0.000192 | 0.631000 | -12.686100 | 0.120698 |
| CH4 | -8.081441 | 0.000003 | 0.657261 | 0.000013 | 0.670300 | -8.182009 | 0.008369 |
| CN | -15.492696 | 0.000012 | 0.273709 | 0.000025 | 0.288800 | -9.469446 | 0.015446 |
| CO | -21.711419 | 0.000010 | 0.400838 | 0.000017 | 0.413700 | -8.070933 | 0.010478 |
| CO2 | -37.789127 | 0.000280 | 0.595973 | 0.000280 | 0.621400 | -15.955684 | 0.175794 |
| CS | -15.804633 | 0.000026 | 0.260602 | 0.000029 | 0.274000 | -8.407530 | 0.018250 |
| Cl2 | -29.976481 | 0.000134 | 0.083918 | 0.000134 | 0.094000 | -6.326863 | 0.084129 |
| ClF | -39.198263 | 0.000065 | 0.088414 | 0.000067 | 0.100100 | -7.333314 | 0.042078 |
| ClO | -30.920322 | 0.000119 | 0.091467 | 0.000119 | 0.104700 | -8.303758 | 0.074797 |
| F2 | -48.381050 | 0.000011 | 0.053916 | 0.000033 | 0.062200 | -5.198481 | 0.020403 |
| H2CO | -22.886870 | 0.000011 | 0.578203 | 0.000018 | 0.596700 | -11.607272 | 0.011035 |
| H2O | -17.232161 | 0.000002 | 0.351502 | 0.000004 | 0.371900 | -12.799685 | 0.002568 |
| H2O2 | -33.162975 | 0.000103 | 0.399743 | 0.000103 | 0.429400 | -18.610108 | 0.064945 |
| H2S | -11.396719 | 0.000001 | 0.282610 | 0.000004 | 0.292000 | -5.892275 | 0.002478 |
| H3COH | -24.097503 | 0.000398 | 0.790750 | 0.000399 | 0.818700 | -17.539036 | 0.250143 |
| H3CSH | -18.272893 | 0.000166 | 0.732690 | 0.000167 | 0.757000 | -15.254781 | 0.104485 |
| HCN | -16.197340 | 0.000001 | 0.479311 | 0.000021 | 0.496900 | -11.037336 | 0.013463 |
| HCO | -22.237063 | 0.000102 | 0.427439 | 0.000103 | 0.444700 | -10.831638 | 0.064768 |
| HCl | -15.610478 | 0.000005 | 0.165154 | 0.000008 | 0.171000 | -3.668681 | 0.004717 |
| HF | -24.874009 | 0.000000 | 0.211399 | 0.000015 | 0.226100 | -9.225112 | 0.009632 |
| HOCl | -31.572985 | 0.000036 | 0.245087 | 0.000037 | 0.264700 | -12.307511 | 0.023157 |
| Li2 | -0.431306 | 0.000048 | 0.039119 | 0.000048 | 0.038900 | 0.137726 | 0.029851 |
| LiF | -24.572038 | 0.000009 | 0.212377 | 0.000018 | 0.222000 | -6.038485 | 0.011269 |
| LiH | -0.786051 | 0.000034 | 0.090914 | 0.000034 | 0.092430 | -0.951129 | 0.021442 |
| N2 | -19.925579 | 0.000008 | 0.343623 | 0.000035 | 0.364600 | -13.163277 | 0.021925 |
| NH | -10.414483 | 0.000006 | 0.124462 | 0.000018 | 0.133500 | -5.671668 | 0.011214 |
| NH2 | -11.064666 | 0.000004 | 0.275602 | 0.000017 | 0.290400 | -9.286012 | 0.010906 |
| NH3 | -11.741160 | 0.000000 | 0.453054 | 0.000017 | 0.475500 | -14.085378 | 0.010649 |
| NO | -25.900393 | 0.000020 | 0.226841 | 0.000026 | 0.244500 | -11.080954 | 0.016437 |
| Na2 | -0.390168 | 0.000066 | 0.026569 | 0.000066 | 0.026800 | -0.144798 | 0.041560 |
| NaCl | -15.276352 | 0.000004 | 0.148271 | 0.000007 | 0.157400 | -5.728608 | 0.004347 |
| O2 | -31.944180 | 0.000053 | 0.179034 | 0.000053 | 0.192400 | -8.387280 | 0.033467 |
| OH | -16.541732 | 0.000004 | 0.160116 | 0.000005 | 0.170200 | -6.327848 | 0.003100 |
| P2 | -13.105438 | 0.000014 | 0.165967 | 0.000026 | 0.186000 | -12.571102 | 0.016616 |
| PH2 | -7.704737 | 0.000000 | 0.236915 | 0.000011 | 0.244000 | -4.445601 | 0.007088 |
| PH3 | -8.340666 | 0.000004 | 0.373802 | 0.000012 | 0.389000 | -9.536878 | 0.007448 |
| S2 | -20.381825 | 0.000029 | 0.149778 | 0.000030 | 0.164000 | -8.924422 | 0.018780 |
| SO | -26.184583 | 0.000246 | 0.185987 | 0.000246 | 0.200700 | -9.232806 | 0.154426 |
| SO2 | -42.262457 | 0.000074 | 0.381287 | 0.000074 | 0.414400 | -20.778582 | 0.046732 |
| Si2 | -7.643107 | 0.004558 | 0.115858 | 0.004558 | 0.121000 | -3.226625 | 2.860189 |
| Si2H6 | -11.360066 | 0.000104 | 0.838559 | 0.000104 | 0.849000 | -6.551537 | 0.065468 |
| SiH2_1A1 | -5.002130 | 0.000004 | 0.240420 | 0.000006 | 0.243000 | -1.619239 | 0.003653 |
| SiH2_3B1 | -4.970075 | 0.000002 | 0.208365 | 0.000005 | 0.210000 | -1.026192 | 0.002970 |
| SiH3 | -5.618663 | 0.000006 | 0.357910 | 0.000008 | 0.363000 | -3.193957 | 0.004849 |
| SiH4 | -6.270622 | 0.000003 | 0.510826 | 0.000005 | 0.515000 | -2.619390 | 0.003405 |
| SiO | -19.937310 | 0.000003 | 0.291113 | 0.000006 | 0.306700 | -9.781036 | 0.004031 |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | 8.43 | 0.39 | -8.43 | 4.87 | 0.07 | | |
#+TBLFM: @>$2='(org-sbe "madformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$3='(org-sbe "maderrformula" (data @5$8..@>>$8) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$6='(org-sbe "sderrformula" (data @5$7..@>>$7) (data_err @5$8..@>>$8) );%0.2f
***** [#B] MAD = 8.43(39)
** pVQZ, BFD
*** CCSD(T)
**** Table
@ -4385,19 +4459,90 @@ plot data u 7:xtic(1) w l notitle, data u :7:8 w err notitle, 1 notitle, -1 noti
#+TBLFM: @>$6='(org-sbe "sderrformula" (data @5$7..@>>$7) (data_err @5$8..@>>$8) );%0.3f
***** MAD = 2.06 +/- 0.35
*** FCI
**** CIPSI
**** CIPSI
***** Table
#+NAME: tz-cipsi-inf
| | e_cal | ae_cal | ae_nr | ae_diff | Ndet |
| | Hartree | Hartree | Hartree | kcal/mol | |
|---------+------------+----------+----------+------------+----------|
|---------+------------+----------+----------+------------+----------|
|---------+------------+----------+----------+------------+----------|
| | | | | | |
#+TBLFM: @>$3='(org-sbe "madformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$5..@>>$5) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$5..@>>$5) );%0.2f
***** MAD =
#+NAME: qz-cipsi-inf
| | Total E | | Delta E | | Reference | Error | |
| | Hartree | | Hartree | | Hartree | kcal/mol | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | e_cal | ae_cal | ae_nr | ae_diff | | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| Be | -1.009626 | 0.000009 | 0.000000 | 0.000012 | | | |
| C | -5.432164 | 0.000004 | 0.000000 | 0.000006 | | | |
| Cl | -14.967668 | 0.000005 | 0.000000 | 0.000007 | | | |
| F | -24.186155 | 0.000003 | 0.000000 | 0.000004 | | | |
| H | -0.499916 | 0.000000 | | 0.000000 | | | |
| Li | -0.196307 | 0.000000 | | 0.000000 | | | |
| N | -9.798444 | 0.000001 | 0.000000 | 0.000002 | | | |
| Na | -0.181980 | 0.000000 | | 0.000000 | | | |
| O | -15.897642 | 0.000002 | 0.000000 | 0.000003 | | | |
| P | -6.476064 | 0.000001 | 0.000000 | 0.000002 | | | |
| S | -10.128682 | 0.000000 | 0.000000 | 0.000001 | | | |
| Si | -3.766939 | 0.000002 | 0.000000 | 0.000002 | | | |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| BeH | -1.588951 | 0.000031 | 0.079409 | 0.000032 | 0.079400 | 0.005936 | 0.019943 |
| C2H2 | -12.499381 | 0.000056 | 0.635222 | 0.000057 | 0.642400 | -4.504129 | 0.035633 |
| C2H4 | -13.749829 | 0.000755 | 0.885838 | 0.000755 | 0.899000 | -8.259487 | 0.473798 |
| C2H6 | -14.976671 | 0.002502 | 1.112848 | 0.002502 | 1.136900 | -15.092883 | 1.570321 |
| CH | -6.064087 | 0.000002 | 0.132008 | 0.000005 | 0.133900 | -1.187362 | 0.002922 |
| CH2_1A1 | -6.716786 | 0.000001 | 0.284791 | 0.000004 | 0.288900 | -2.578570 | 0.002633 |
| CH2_3B1 | -6.731323 | 0.000002 | 0.299328 | 0.000004 | 0.304100 | -2.994534 | 0.002764 |
| CH3 | -7.415727 | 0.000020 | 0.483816 | 0.000020 | 0.490800 | -4.382561 | 0.012661 |
| CH3Cl | -22.521516 | 0.001709 | 0.621936 | 0.001709 | 0.631000 | -5.687506 | 1.072221 |
| CH4 | -8.093853 | 0.000056 | 0.662026 | 0.000056 | 0.670300 | -5.192118 | 0.035136 |
| CN | -15.513348 | 0.000021 | 0.282740 | 0.000022 | 0.288800 | -3.802447 | 0.013682 |
| CO | -21.738670 | 0.000219 | 0.408865 | 0.000219 | 0.413700 | -3.034243 | 0.137599 |
| CO2 | -37.838700 | 0.001069 | 0.611253 | 0.001069 | 0.621400 | -6.367363 | 0.670811 |
| CS | -15.829917 | 0.000200 | 0.269071 | 0.000200 | 0.274000 | -3.092953 | 0.125661 |
| Cl2 | -30.027659 | 0.000014 | 0.092322 | 0.000017 | 0.094000 | -1.052786 | 0.010930 |
| ClF | -39.249390 | 0.000609 | 0.095566 | 0.000609 | 0.100100 | -2.844986 | 0.382114 |
| ClO | -30.966211 | 0.000499 | 0.100901 | 0.000499 | 0.104700 | -2.383929 | 0.313427 |
| F2 | -48.431244 | 0.000054 | 0.058933 | 0.000054 | 0.062200 | -2.050000 | 0.033800 |
| H2CO | -22.917424 | 0.000211 | 0.587787 | 0.000211 | 0.596700 | -5.593292 | 0.132435 |
| H2O | -17.256113 | 0.000011 | 0.358639 | 0.000011 | 0.371900 | -8.321241 | 0.006951 |
| H2O2 | -33.206043 | 0.000566 | 0.410928 | 0.000566 | 0.429400 | -11.591315 | 0.355078 |
| H2S | -11.416822 | 0.000036 | 0.288308 | 0.000036 | 0.292000 | -2.316961 | 0.022567 |
| H3COH | -24.126733 | 0.000210 | 0.797264 | 0.000210 | 0.818700 | -13.451386 | 0.131821 |
| H3CSH | -18.303106 | 0.000888 | 0.742596 | 0.000888 | 0.757000 | -9.038560 | 0.557191 |
| HCN | -16.220238 | 0.000114 | 0.489715 | 0.000114 | 0.496900 | -4.508747 | 0.071423 |
| HCO | -22.265628 | 0.000503 | 0.435907 | 0.000503 | 0.444700 | -5.517539 | 0.315588 |
| HCl | -15.636332 | 0.000018 | 0.168747 | 0.000019 | 0.171000 | -1.413491 | 0.011743 |
| HF | -24.902433 | 0.000009 | 0.216362 | 0.000010 | 0.226100 | -6.110912 | 0.006124 |
| HOCl | -31.621625 | 0.000224 | 0.256399 | 0.000224 | 0.264700 | -5.208797 | 0.140532 |
| Li2 | -0.431443 | 0.000004 | 0.038829 | 0.000004 | 0.038900 | -0.044823 | 0.002472 |
| LiF | -24.599582 | 0.000001 | 0.217120 | 0.000003 | 0.222000 | -3.062355 | 0.001982 |
| LiH | -0.787778 | 0.000003 | 0.091555 | 0.000003 | 0.092430 | -0.549078 | 0.002108 |
| N2 | -19.952215 | 0.000053 | 0.355328 | 0.000053 | 0.364600 | -5.818524 | 0.033494 |
| N2H4 | -22.265086 | 0.002365 | 0.668535 | 0.002365 | 0.699600 | -19.493818 | 1.484256 |
| NH | -10.426353 | 0.000005 | 0.127994 | 0.000005 | 0.133500 | -3.455183 | 0.003041 |
| NH2 | -11.080314 | 0.000014 | 0.282038 | 0.000014 | 0.290400 | -5.247264 | 0.008675 |
| NH3 | -11.759748 | 0.000007 | 0.461556 | 0.000007 | 0.475500 | -8.749893 | 0.004378 |
| NO | -25.932141 | 0.000214 | 0.236056 | 0.000214 | 0.244500 | -5.298782 | 0.134282 |
| Na2 | -0.390671 | 0.000016 | 0.026711 | 0.000016 | 0.026800 | -0.055830 | 0.010216 |
| NaCl | -15.303431 | 0.000049 | 0.153783 | 0.000049 | 0.157400 | -2.269973 | 0.030858 |
| O2 | -31.982234 | 0.000316 | 0.186951 | 0.000316 | 0.192400 | -3.419459 | 0.198515 |
| OH | -16.562097 | 0.000014 | 0.164539 | 0.000014 | 0.170200 | -3.552177 | 0.008780 |
| P2 | -13.130791 | 0.000179 | 0.178662 | 0.000179 | 0.186000 | -4.604850 | 0.112434 |
| PH2 | -7.718213 | 0.000026 | 0.242316 | 0.000026 | 0.244000 | -1.056595 | 0.016381 |
| PH3 | -8.356876 | 0.000003 | 0.381064 | 0.000003 | 0.389000 | -4.980126 | 0.001736 |
| S2 | -20.417704 | 0.000461 | 0.160340 | 0.000461 | 0.164000 | -2.296869 | 0.289383 |
| SO | -26.223097 | 0.000334 | 0.196773 | 0.000334 | 0.200700 | -2.464276 | 0.209887 |
| SO2 | -42.324964 | 0.005165 | 0.400998 | 0.005165 | 0.414400 | -8.409757 | 3.241071 |
| Si2 | -7.650009 | 0.000173 | 0.116131 | 0.000173 | 0.121000 | -3.055403 | 0.108497 |
| Si2H6 | -11.392075 | 0.006207 | 0.858701 | 0.006207 | 0.849000 | 6.087500 | 3.894679 |
| SiH2_1A1 | -5.011004 | 0.000002 | 0.244233 | 0.000003 | 0.243000 | 0.773601 | 0.001672 |
| SiH2_3B1 | -4.978375 | 0.000002 | 0.211604 | 0.000003 | 0.210000 | 1.006802 | 0.001850 |
| SiH3 | -5.629378 | 0.000037 | 0.362691 | 0.000037 | 0.363000 | -0.194032 | 0.022952 |
| SiH4 | -6.283377 | 0.000026 | 0.516774 | 0.000026 | 0.515000 | 1.113385 | 0.016341 |
| SiO | -19.966280 | 0.000114 | 0.301700 | 0.000114 | 0.306700 | -3.137770 | 0.071685 |
|---------+------------+----------+----------+----------+-----------+------------+----------|
| | 4.51 | 0.78 | -4.18 | 4.19 | 0.20 | | |
#+TBLFM: @>$2='(org-sbe "madformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$3='(org-sbe "maderrformula" (data @5$8..@>>$8) );%0.2f
#+TBLFM: @>$4='(org-sbe "mudformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$5='(org-sbe "sdformula" (data @5$7..@>>$7) );%0.2f
#+TBLFM: @>$6='(org-sbe "sderrformula" (data @5$7..@>>$7) (data_err @5$8..@>>$8) );%0.2f
***** MAD = 4.51(78)
** SHCI CBS extrpolation
#+NAME: cbs-shci
| | e_cal | ae_cal | ae_nr | ae_diff |

30
Manuscript/rsdft-cipsi-qmc.tex
View File

@ -709,7 +709,7 @@ RS-DFT-CIPSI & 0 & 4.53 & -1.66
\phantom{} & 1 & 17.07 & -16.92 & 9.83 & 9.06 & -9.06 & 5.88 & --- & --- & --- \\
\phantom{} & 2 & 19.20 & -19.05 & 10.91 & --- & --- & --- & --- & --- & --- \\
\phantom{} & 5 & 22.93 & -22.79 & 13.24 & --- & --- & --- & --- & --- & --- \\
\phantom{} & \(\infty\) & 23.62 & -23.48 & 12.81 & --- & --- & --- & --- & --- & --- \\
\phantom{} & \(\infty\) & 23.63(4) & -23.49(4) & 12.81(4) & 8.43(39) & -8.43(39) & 4.87(7) & 4.51(78) & -4.18(78) & 4.19(20) \\
\hline
DMC@RS-DFT-CIPSI & 0 & 4.61(\phantom{0.}34) & -3.62(\phantom{0.}34) & 5.30(\phantom{0.}09) & 3.52(19) & -1.03(19) & 4.39(04) & 3.16(26) & -0.12(26) & 4.12(03) \\
\phantom{} & 1/4 & 4.04(\phantom{0.}37) & -3.13(\phantom{0.}37) & 4.88(\phantom{0.}10) & 3.39(77) & -0.59(77) & 4.44(34) & 2.90(25) & 0.25(25) & 3.745(5) \\
@ -734,8 +734,10 @@ For comparison, we have computed the energies of all the atoms and
molecules at the DFT level with different density functionals, and at
the CCSD(T) level. Table~\ref{tab:mad} gives the corresponding mean
absolute errors (MAE), mean signed errors (MSE) and standard
deviations (RMSD). For FCI (RS-DFT-CIPSI, $\mu=\infty$), we have
given extrapolated values at $\EPT\rightarrow 0$.
deviations (RMSD). For FCI (RS-DFT-CIPSI, $\mu=\infty$) we have
given extrapolated values at $\EPT\rightarrow 0$, and the error bars
correspond to the difference between the energies computed with a
two-point and with a three-point linear extrapolation.
In this benchmark, the great majority of the systems are well
described by a single determinant. Therefore, the atomization energies
@ -763,11 +765,12 @@ underestimated. This confirms that some of the basis-set
incompleteness error is transferred in the fixed-node error.
Within the double-zeta basis set, the calculations could be done for the
whole range of values of $\mu$, and the optimal value of $\mu$ was
estimated for each system by searching for the minimum of the spline
interpolation curve of the FN-DMC energy as a function of $\mu$.
This corresponds the the line labelled by the \emph{Opt} value of $\mu$
in the table. Using the optimal value of $\mu$ clearly improves the
whole range of values of $\mu$, and the optimal value of $\mu$ for the
trial wave function was estimated for each system by searching for the
minimum of the spline interpolation curve of the FN-DMC energy as a
function of $\mu$.
This corresponds the the line of the table labelled by the \emph{Opt}
value of $\mu$. Using the optimal value of $\mu$ clearly improves the
MAE, the MSE an the RMSD compared the the FCI wave function. This
result is in line with the common knowledge that re-optimizing
the determinantal component of the trial wave function in the presence
@ -776,6 +779,17 @@ These calculations were done only for the smallest basis set
because of the expensive computational cost of the QMC calculations
when the trial wave function is expanded on more than a few million
determinants.
At the RS-DFT-CIPSI level, we can remark that with the triple-zeta
basis set the MAE are larger for $\mu=1$~bohr$^{-1}$ than for the
FCI. For the largest systems, as shown in figure~\ref{fig:g2-ndet}
there are many systems which did not reach the threshold
$\EPT<1$~m\hartree{}, and the number of determinants exceeded
10~million so the calculation stopped. In this regime, there is a
small size-consistency error originating from the imbalanced
truncation of the wave functions, which is not present in the
extrapolated FCI energies. The same comment applies to
$\mu=0.5$~bohr$^{-1}$ with the quadruple-zeta basis set.
\begin{figure}
\centering