Prime Minister David Cameron is travelling to Scotland for talks with First Minister Alex Salmond.
Mr Cameron, who is making good his pledge to head north within days of an election victory, has promised to treat the devolved government with "respect".
Mr Salmond will press the prime minister to concede further cash and spending powers for Holyrood.
Mr Cameron wants a "new spirit of co-operation" between the Scottish Parliament and Westminster as a whole.
The head of the UK’s new Tory-Lib Dem government is also meeting Scottish opposition leaders.
Mr Salmond will call on Mr Cameron to bring forward £350m of capital spending to aid Scotland’s economic recovery, and will also argue Scotland is owed £165m over five years in "consequential" funding, as a result of public spending in relation to the London Olympics.
The SNP leader will also request the Treasury releases cash for Scotland held in the fossil fuel levy, worth £180m, and will press the case to give enhanced borrowing powers to Holyrood, as recommended by the Calman Commission review of devolution.
Mr Cameron will be accompanied by Danny Alexander, the Liberal Democrat MP who has been appointed Scottish secretary.
The visit comes after Scottish Tory leader Annabel Goldie said the public had grown tired of past rows between the Scottish and UK governments, which have often focussed on funding, the proposed independence referendum and more powers for the Scottish Parliament.
The prime minister has said Westminster would not seek to override Holyrood’s role on devolved matters, but also stressed the Scottish government must respect areas reserved to the UK parliament.
Mr Salmond said he would always support UK government policies which were in the "interest of the Scottish people", but added SNP ministers would, at all times, be making the argument to "advance the cause of Scotland".
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