Ajax were due to play Heerenveen away, however the match fell victim to the weather allowing PSV the chance to regain top spot.
Three goals in the space of 25 minutes from Jurgen Colin, John de Jong and Jan Vennegoor of Hesselink put the home side in cruise control early on.
Andrew de Riddler replied immediately but that was a good as it got for the visitors with Hesselink adding a second before Johann Vonlathen put the icing on the cake with a fifth.
Feyenoord climbed to third in the table following a 2-1 away win over NEC Nijmegen.
Andrzej Niedzielan put the home side ahead after 24 minutes, however goals either side of the break from Dirk Kuyt and Thomas Buffel sealed the points for the visitors.
AZ will feel they dropped two points following the scoreless home draw Willem II, while NAC Breda's home clash with Groningen was suspended after 16 minutes due to snow.
Elsewhere, former Leeds defender Robert Molenaar bagged all three points for RBC Roosendaal against Utrecht with an 83rd minute winner at Nieuw Galgewaard.
Vitesse moved ahead of Volendam despite gaining just a point from their goalless trip to Twente as RKC Waalwijk ran out 4-0 winners at the Veronica Stadion.
Volendam were level at the break but second half goals from Yuri Cornelisse, Said Boutahar, Robert Fuchs and Iwan Redan ensured they suffered their 11th defeat of the campaign.
ADO Den Haag's home clash against Roda also fell victim to adverse weather conditions.
Click below for match summaries:
Den Haag P-P Roda
AZ 0-0 Willem II
Twente 0-0 Vitesse
Utrecht 0-1 RBC
Volendam 0-4 RKC
Heerenveen P-P Ajax
NAC P-P Groningen
NEC 1-2 Feyenoord
PSV 5-1 Zwolle
Click here for the latest Dutch Eredivisie table.
