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<div>I am having a weird result when comparing results for basis sets from the internal basis set library and from explicitly including the same basis set in the input file. While the results converge to the same value of RHF energy, the initial guess is different.</div>
<div> </div>
<div>For example, for F- in a cc-pVDZ basis including the basis set explicitly:</div>
<div>***,F- cc-pVDZ explicitly</div>
<div>memory,400,M</div>
<div>basis={</div>
<div>s, F , 14710.0000000, 2207.0000000, 502.8000000, 142.6000000, 46.4700000, 16.7000000, 6.3560000, 1.3160000, 0.3897000</div>
<div>c, 1.9, 0.0007210, 0.0055530, 0.0282670, 0.1064440, 0.2868140, 0.4486410, 0.2647610, 0.0153330, -0.002332</div>
<div>c, 1.9, -0.0001650, -0.0013080, -0.0064950, -0.0266910, -0.0736900, -0.1707760, -0.1123270, 0.5628140, 0.568778</div>
<div>c, 9.9, 1</div>
<div>p, F , 22.6700000, 4.9770000, 1.3470000, 0.3471000</div>
<div>c, 1.4, 0.0448780, 0.2357180, 0.5085210, 0.45812</div>
<div>c, 4.4, 1</div>
<div>d, F , 1.6400000</div>
<div>c, 1.1, 1</div>
<div>}</div>
<div>thrdscf=1e-12,thrdscf_max=1e-9</div>
<div>gthresh,throvl=1e-9,throrth=1e-7</div>
<div>gdirect</div>
<div>geometry={f;</div>
<div>}</div>
<div>charge=-1</div>
<div>hf</div>
<div> </div>
<div>has the following set of iterations:</div>
<div>ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS CPU(IT) CPU(TOT)</div>
<div> 1 0.000D+00 0.000D+00 -99.29578519 95.175396 0.000000 0.000000 0.000000 0 5.7 9.2 diag</div>
<div> 2 0.000D+00 0.131D+00 -99.34548119 88.831609 0.000000 0.000000 0.000000 1 3.0 12.2 diag</div>
<div> 3 0.206D+00 0.728D-01 -99.36598299 91.014455 0.000000 0.000000 0.000000 2 3.1 15.2 diag</div>
<div> 4 0.688D-01 0.506D-03 -99.36598357 91.025429 0.000000 0.000000 0.000000 3 3.0 18.2 diag</div>
<div> 5 0.401D-03 0.113D-04 -99.36598357 91.025398 0.000000 0.000000 0.000000 3 3.0 21.2 diag</div>
<div> 6 0.184D-04 0.259D-05 -99.36598357 91.025417 0.000000 0.000000 0.000000 3 2.0 23.2 diag</div>
<div> 7 0.558D-05 0.141D-06 -99.36598357 91.025424 0.000000 0.000000 0.000000 0 2.0 25.1 orth</div>
<div> </div>
<div>While calling the same basis set from the internal library,</div>
<div>***,F- cc-pVDZ implicitly</div>
<div>memory,400,M</div>
<div>basis={</div>
<div>f=cc-pVDZ</div>
<div>}</div>
<div>thrdscf=1e-12,thrdscf_max=1e-9</div>
<div>gthresh,throvl=1e-9,throrth=1e-7</div>
<div>gdirect</div>
<div>geometry={f;</div>
<div>}</div>
<div>charge=-1</div>
<div>hf</div>
<div> </div>
<div>has the following iteration set:</div>
<div>ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS CPU(IT) CPU(TOT)</div>
<div> 1 0.000D+00 0.000D+00 -99.29785341 95.113039 0.000000 0.000000 0.000000 0 5.4 7.5 diag</div>
<div> 2 0.000D+00 0.129D+00 -99.34608743 88.864010 0.000000 0.000000 0.000000 1 2.9 10.3 diag</div>
<div> 3 0.202D+00 0.717D-01 -99.36598302 91.014701 0.000000 0.000000 0.000000 2 2.8 13.1 diag</div>
<div> 4 0.678D-01 0.494D-03 -99.36598357 91.025427 0.000000 0.000000 0.000000 3 3.1 16.2 diag</div>
<div> 5 0.392D-03 0.110D-04 -99.36598357 91.025398 0.000000 0.000000 0.000000 3 3.1 19.3 diag</div>
<div> 6 0.179D-04 0.252D-05 -99.36598357 91.025417 0.000000 0.000000 0.000000 3 3.1 22.4 diag</div>
<div> 7 0.542D-05 0.138D-06 -99.36598357 91.025424 0.000000 0.000000 0.000000 0 3.0 25.4 orth</div>
<div> </div>
<div>Looking at the first iteration there is a difference of 2 mH. In this case, that isn’t a big deal, however, I have added basis sets to the basis set library and for some larger basis sets, the resultant iterations converge to different states. I can send
those examples as desired. Can someone explain why this behavior is occurring and how to control it?</div>
<div> </div>
<div>These calculations were run with molpro version 2009.1, patch level 29.</div>
<div> </div>
<div>Thanks,</div>
<div>Andrew</div>
<div> </div>
<div>---</div>
<div>Andrew G. Taube</div>
<div>D. E. Shaw Research</div>
<div>email: Andrew.Taube@DEShawResearch.com</div>
<div>Tel: +1-212-478-0118</div>
<div>Fax: +1-212-845-1118</div>
<div> </div>
<div> </div>
<div> </div>
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