Dear CP2K community,<div><br /></div><div>I am trying to run <b>constrained DFT calculations</b> in CP2K 2024.2 to calculate the electron transfer parameters of the following reaction in an implicit DMF environment:</div><div><b>[trans-stilbene]- + 2bromophenol ------------> trans-stilbene + [2-bromophenol]-</b></div><div><br /></div><div>1) I have observed that <b>the SCF wavefunction optimization keeps on fluctuating</b>, even though I am restarting my calculation from an already optimized wavefunction under similar conditions (but without any charge constraint).</div><div>2) In other similar reactions, I have observed that even if the wavefunction reaches optimization somehow - <b>the charges do not reach the appropriate constraint target value. </b>The iterations are either too slow to reach convergence or start to give a drastically wrong number of valence electrons.</div><div><br /></div><div>Here is the CDFT section i am using:</div><div> &CDFT<br /> TYPE_OF_CONSTRAINT HIRSHFELD<br /> ATOMIC_CHARGES TRUE<br /> COUNTER 0<br /> STRENGTH ${CDFT_STRENGTH}<br /> TARGET ${CDFT_TARGET}<br /> &ATOM_GROUP<br /> ATOMS ${CDFT_ATOMS}<br /> COEFF ${CDFT_COEFF}<br /> CONSTRAINT_TYPE CHARGE<br /> &END ATOM_GROUP<br /> &DUMMY_ATOMS<br /> ATOMS ${CDFT_DUMMY}<br /> &END DUMMY_ATOMS<br /> &OUTER_SCF ON<br /> TYPE CDFT_CONSTRAINT<br /> EXTRAPOLATION_ORDER 2<br /> MAX_SCF 50<br /> EPS_SCF 1.0E-3<br /> OPTIMIZER BROYDEN<br /> STEP_SIZE -2.0<br /> &CDFT_OPT ON<br /> BROYDEN_TYPE BT1_LS<br /> MAX_LS 5<br /> CONTINUE_LS<br /> FACTOR_LS 0.5<br /> JACOBIAN_STEP 1.0E-2<br /> JACOBIAN_FREQ 1 1<br /> JACOBIAN_TYPE FD1<br /> JACOBIAN_RESTART .FALSE.<br /> &END CDFT_OPT<br /> &END OUTER_SCF<br /> &HIRSHFELD_CONSTRAINT<br /> SHAPE_FUNCTION GAUSSIAN<br /> GAUSSIAN_SHAPE VDW<br /> &END HIRSHFELD_CONSTRAINT<br /> &PROGRAM_RUN_INFO ON<br /> &EACH<br /> QS_SCF 1<br /> &END EACH<br /> COMMON_ITERATION_LEVELS 2<br /> ADD_LAST NUMERIC<br /> FILENAME ./${NAME}<br /> &END PROGRAM_RUN_INFO<br /> &END CDFT<br /></div><div><br /></div><div>Could you please help me figure out what is causing these issues? I have attached my input and output files for your reference.</div><div><br /></div><div>I really appreciate all your time and help. Thank you,</div><div>Akanksha</div><div><br /></div><div>P.S. This question is a repost as I was not very clear in my previous post and didn't get a response. Sorry about that!</div><div><br /></div>
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